Polyfluoroallyloxy compounds, their preparation and copolymers therefrom

ABSTRACT

The reaction of a polyfluorocarbonyl compound such as a polyfluoroketone or polyfluorocarboxylic acid fluoride with fluoride ion and a polyfluoroallyl chloride, bromide or fluorosulfate produces a polyfluoroallyloxy carboxylic acid or ester, e.g., CF 2  ═CFCF 2  OCF 2  CF 2  COOH. The polyfluoroallyloxy compounds copolymerize with ethylenically unsaturated monomers such as tetrafluoroethylene, chlorotrifluoroethylene or vinylidene fluoride to form polymers which are moldable, and in some cases electrically conducting or are water-wettable and dyeable.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of application Ser. No.020,354, filed Mar. 14, 1979, now abandoned, which in turn is acontinuation-in-part of application Ser. No. 850,729, filed Nov. 11,1977, now abandoned, which is in turn a continuation-in-part ofapplication Ser. No. 747,029, filed Dec. 2, 1976 by Carl George Krespan,now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to polyfluoroallyloxy compounds, processes fortheir preparation and copolymers prepared therefrom.

2. Relation to the Prior Art

1. U.S. Pat. No. 2,856,435 to E. S. Lo discloses the preparation ofperfluoroallyloxy-1,1-dihydroperfluoroalkanes from3-chloropentafluoropropene and a 1,1-dihydroperfluoroalkanol in alkalinemedium, e.g. ##STR1##

2. U.S. Pat. No. 2,671,799 to W. T. Miller discloses a process forreplacing the chlorine in perfluoroallyl chloride(3-chloropentafluoropropene) with methoxy, cyano, iodo and nitrategroups, e.g.

    CF.sub.2 ═CFCF.sub.2 Cl+NaOCH.sub.3 →CF.sub.2 ═CFCF.sub.2 OCH.sub.3

3. M. E. Redwood and C. J. Willis, Canad. J. Chem., 45, 389 (1967)describe the reaction of allyl bromide with cesiumheptafluoro-2-propoxide to form 2-allyloxyheptafluoropropane:

    CH.sub.2 ═CHCH.sub.2 Br+(CF.sub.3).sub.2 CFO.sup.- Cs.sup.+ →CH.sub.2 ═CHCH.sub.2 OCF(CF.sub.3).sub.2 +CsBr

4. J. A. Young, Fluorine Chemistry Reviews, 1, 389-393 (1967) surveysthe formation of perfluoroalkoxide anions by the action of alkali metalfluorides on perfluoroketones, perfluoroalkyloxiranes,perfluorocarboxylic acid fluorides and perfluoroalkyl fluorosulfates.References 5-9 which follow are examples of the nucleophilic reactionsof perfluoroalkoxide anions.

5. U.S. Pat. No. 3,450,684 to R. A. Darby discloses the preparation offluorocarbon polyethers and their polymers by reaction ofperfluoroalkanoyl fluorides with potassium or quaternary ammoniumfluoride and hexafluoropropene epoxide. ##STR2##

6. U.S. Pat. No. 3,674,820 to A. G. Pittman and W. L. Wasley disclosesthe reaction of fluoroketones with an alkali metal fluoride and anomega-haloalkanoic acid ester to form an omega-(perfluoroalkoxy)alkanoic acid ester, e.g.

    (CF.sub.3).sub.2 CO+KF+Br(CH.sub.2).sub.4 CO.sub.2 CH.sub.3 →(CF.sub.3).sub.2 CFO(CH.sub.2).sub.4 CO.sub.2 CH.sub.3

7. U.S. Pat. No. 3,795,684 to E. Domba also discloses the reaction ofhexafluoroacetone with potassium fluoride and an omega-haloalkanoic acidester.

8. U.S. Pat. No. 3,527,742 to A. G. Pittman and W. L. Wasley, disclosesthe reduction of the compounds of Reference 6 to the correspondingalcohols and their esterification to polymerizable acrylates.

9. U.S. Pat. No. 3,799,992 to A. G. Pittman and W. L. Wasley disclosesthe preparation of (perfluoroalkoxy)vinyl compounds by reaction of aperfluoroketone with an alkali metal fluoride and a 1,2-dihaloethane,followed by dehydrohalogenation of the intermediate2-perfluoroalkoxyhaloethane. ##STR3##

10. U.S. Pat. No. 3,321,532 to C. E. Lorenz discloses the rearrangementof perfluoro-2-alkoxyalkanoyl fluorides to perfluoroalkoxyolefins bypassage over a metal oxide at 100°-400° C., e.g., ##STR4##

11. U.S. Pat. No. 3,467,638 to D. B. Pattison discloses polyfluorovinylethers of the formula ##STR5## where n is 1 or 2 and copolymerscontaining said ethers.

12. L. S. Kobrina, Fluorine Chemistry Reviews, vol. 7, p. 67, MarcelDekker, Inc., N.Y. (1974), discloses the substitution of hydroxyl into--OC₆ F₅ groups to form --OC₆ F₄ OH.

13. U.S. Pat. No. 4,131,740 to D. C. England discloses the compoundROOC-CF₂ -COF, hexafluoropropene oxide adducts with the formula ##STR6##vinyl ethers prepared from same, of the formula ##STR7## and copolymersprepared from said vinyl ethers; n is 1 to 6, and R is CH₃ or C₂ H₅.

14. U.S. Pat. No. 4,138,426 to D. C. England discloses the nitrile##STR8## where n is 1 to 6.

SUMMARY OF THE INVENTION

According to the present invention there is provided apolyfluoroallyloxy compound having the formula ##STR9## wherein X is--Cl or --F, and R_(F) is: ##STR10## wherein R¹ is a carbon-carbon bondor a linear or branched perfluoroalkylene group of 1 to 12 carbon atoms;Q is --SO₂ F, --COF, --F, --Cl, --Br, --I, --CN, --CO₂ H, --OCF₂ CF═CF₂,--OC₆ F₅, or --CO₂ R⁴ where R⁴ is --CH₃ or --C₂ H₅ ; Y and Y',independently, are --F or --CF₃ and only Y or Y' can be --CF₃ ; or

    --CF(R.sup.2).sub.2                                        (ii)

wherein R² is --F, --CF₂ Cl, --CF₂ CN, --CF₂ COF, --CF₂ CO₂ H, --CF₂OCF(CF₃)₂ or --CF₂ CO₂ R⁴ where R⁴ is defined as above; or ##STR11##wherein R³ is a linear or branched perfluoroalkylene group of carboncontent such that the moiety ##STR12## does not exceed 15 carbon atoms;Y is --F or --CF₃ ; n is 1 to 4; and Q' is defined as for Q above; or##STR13## wherein G is --COF, --CO₂ H or --CO₂ R⁴ where R⁴ is --CH₃ or--C₂ H₅.

There is also provided a process for preparing a polyfluoroallyloxycompound which comprises:

(1) mixing and reacting

(a) a carbonyl compound having the formula: ##STR14## wherein A¹ is##STR15## where R¹ is a carbon-carbon bond or a linear or branchedperfluoroalkylene group of 1 to 12 carbon atoms; Q" is --SO₂ F, --SO₂OCF₂ CH₃, --OCF₂ CF═CF₂, --COF, --F, --Cl, --Br, --I, --CN, --OC₆ F₅ or--CO₂ R⁴ is --CH₃ or --C₂ H₅ ; Y and Y', independently, are --F or --CF₃and only Y or Y' can be --CF₃ ; or

(b) a carbonyl compound having the formula: ##STR16## wherein A² is##STR17## where R³ is a linear or branched perfluoroalkylene group ofcarbon content such that the moiety ##STR18## does not exceed 14 carbonatoms; Y is --F or --CF₃ ; n is 1 to 4; and Q" is defined as above; or

(c) a carbonyl compound having the formula: ##STR19## wherein R² is --F,--CF₂ Cl, --CF₂ CN, --CF₂ COF, --CF₂ CO₂ H, --CF₂ OCF(CF₃)₂ or --CF₂ CO₂R⁴ where R⁴ is --CH₃ or --C₂ H₅,

with a metal fluoride of the formula MF where M is K--, Rb--, Cs--, orR₄ N--where each --R, alike or different, is alkyl of 1 to 6 carbonatoms; and

(2) mixing the mixture from (1) with a perfluoroallyl compound of theformula ##STR20## wherein X is --Cl or --F; and

Z is --Cl, --Br or --OSO₂ F.

Also provided is a copolymer of the aforesaid polyfluoroallyloxycompound with at least one ethylenically unsaturated monomer.

DETAILS OF THE INVENTION

This invention relates to compounds of formulae 4, 7, 9, and 10,prepared from starting materials 1, 2 and either 3, 6, 8, or 8'according to the following equations: ##STR21## the terminal --COF groupin 10 being convertible to the groups --CO₂ H and --CO₂ R⁴ where R⁴ is--CH₃ or --C₂ H₅.

In the above equations, starting materials 1, 2, and either 3, 6, 8, or8' react to give products 4, 7, 9, or 10, respectively, and a metal salt5. The symbols A, R¹, R², R³, M, n, Q, Q', X, Y, Y' and Z are as givenin the Summary. Products represented by general structures 4, 7, 9, and10 can be converted into useful copolymers especially withtetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene andprovided tetrafluoroethylene or vinylidene fluoride is also presentperfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), andhexafluoropropylene.

Preferred polyfluoroallyloxy compounds of formula 4 are those in whichR¹ is a carbon-carbon bond or a linear or branched perfluoroalkyl groupof 1 to 12 carbon atoms and Q is --SO₂ F, --COF, --F, --Cl, --Br, --CN,--OC₆ F₅, --OCF₂ CF═CF₂, --CO₂ H and --CO ₂ R⁴ where R⁴ is --CH₃ or --C₂H₅ ; and X is --F.

Especially preferred polyfluoroallyloxy compounds of formula 4 are thosein which R¹ is a carbon-carbon bond or linear perfluoroalkyl and Q is--SO₂ F, --COF, --CN or --CO₂ R⁴ ; and X is --F.

Preferred polyfluoroallyloxy compounds of formula 7 are those in whichR³ is linear; Q' is --SO₂ F, --COF, --CN or --CO₂ R⁴ ; and X is --F.

Preferred polyfluoroallyloxy compounds of formula 9 are those in whichR² is --CF₂ COF, --CF₂ CN, or --CF₂ CO₂ R⁴ ; and X is --F.

The polyfluoroallyl group of the products 4, 7, 9 and 10 is derived fromthe corresponding polyfluoroallyl chloride, bromide or fluorosulfate 1by nucleophilic displacement of the chloride, bromide or fluorosulfategroup with a preformed polyfluoroalkoxide anion derived from the metalfluoride 2 and the carbonyl compound 3, 6, or 8. The synthesis is thus aone-vessel sequential addition of reagents, 3, 6 or 8 and 1 to asuspension or solution of 2 in a suitable solvent.

Polyfluoroallyl fluorosulfates are the preferred reagents for thisdisplacement, and they can be prepared conveniently by treatment ofpolyfluoroalkenes with sulfur trioxide, as described in coassignedapplication Ser. No. 718,337, filed Aug. 27, 1976, in the name of D. C.England, now abandoned. Such reactions are typically carried out insealed Carius tubes at temperatures of 25°-90° C. for periods of 16hours to 4 days, and the product fluorosulfates are purified byfractional distillation. A preparation of the preferred perfluoroallylfluorosulfate (pentafluoro-2-propenyl fluorosulfate) is given in Example2.

Stable metal polyfluoroalkoxides are formed by the reaction of certainmetal fluorides with polyfluorinated ketones and acid fluorides (J. A.Young, loc. cit.), thus: ##STR22## The usefulness of such intermediatepolyfluoroalkoxides is determined by their stability, as measured bytheir ease of thermal decomposition. Because their formation isreversible, the equilibrium concentrations of various species in a givenreaction mixture are important quantities which determine whether or notthe subsequent displacement will occur to form product 4, 7, 9, or 10.Solutions in which the equilibrium lies towards the right (highconcentration of anion) will be more effective than those in which itlies towards the left (high concentration of carbonyl compound).

Polyfluoroalkoxide anion formation and chemistry is dependent upon thefollowing four conditions, discussed in further detail by J. A. Young,loc. cit., F. W. Evans, M. H. Litt, A. M. Weidler-Kubanek and F. P.Avonda, J. Org. Chem., 33, 1837, 1839 (1968), and M. A. Redwood and C.J. Willis, Canad. J. Chem., 45, 389 (1967). (1) Stablepolyfluoroalkoxide anions are formed when the carbonyl compound ishighly fluorinated because the electron-withdrawing effect of thefluorine atoms distributes the negative charge over the entire anion.Substitution of some of the fluorine by chlorine, other fluoroalkylgroups or hydrogen destablizes the anion because these groups are lesselectron-withdrawing and the negative charge is not as readilyaccommodated. (2) Large cations such as K⁺, Rb⁺, Cs⁺ and R₄ N⁺ favor theformation of stable polyfluoroalkoxides more than small cations such asLi⁺ and Na⁺ because the lattice energy of metallic fluorides isinversely proportional to cation size. In other words, large cation sizeand small lattice energy favors disruption of the metallic fluoridecrystal structure to form the anion. (3) Solvents which have a high heatof solution for the polyfluoroalkoxide favor its formation. Aproticpolar solvents such as N,N-dimethylformamide (DMF), acetonitrile, and1,2-dimethoxyethane (glyme) are very effective for this purpose. (4)When there are fluorine atoms alpha to the oxygen atom in the anion,loss of fluoride ion may compete with the desired reactions, e.g.,

    ______________________________________                                         ##STR23##    has no α-fluorine to lose and forms many stable                         derivatives.                                                     ##STR24##    requires a reactive compound such as allyl bromide for                        nucleophilic substitution.                                      CF.sub.3 O.sup.-                                                                            usually eliminates F.sup.- ; nucleophilic                                     substitution is shown with per-                                               fluoroallyl fluorosulfate in                                                  Example 20.                                                     ______________________________________                                    

In the practice of this invention, the polyfluoroalkoxide anion ispreferably preformed by the addition of the carbonyl compound to astirred mixture of the metal fluoride in a suitable aprotic solvent. Thecompleteness of formation of the anion is generally signalled by theextent to which the metal fluoride dissolves in the solvent as thereaction progresses. The stoichiometry of polyfluoroalkoxide anionformation requires one molar equivalent of metal fluoride for eachcarbonyl group which is converted to its anion, e.g.: ##STR25##

The presence of up to a twice-molar excess of metal fluoride isgenerally not detrimental. Two side effects of excess metal fluorideare: (1) to hinder the observation of the reaction endpoint because ofthe presence of undissolved solid in the reaction mixture, and (2)excess fluoride ion in solution may react directly with perfluoroallylfluorosulfate to form hexafluoropropene.

Because of the limited thermal stability of polyfluoroalkoxides, theirformation is usually accomplished between -20° C. and +60° C.,preferably with external cooling to maintain the temperature between 0°C. and 10° C.

The time required to complete polyfluoroalkoxide formation varies withthe carbonyl component, but it is preferably from 0.5 to 2 hours, eachindividual case being usually determined by how long it takes thereaction mixture to become homogeneous.

N,N-Dimethylformamide (DMF), acetonitrile, N,N-dimethylacetamide (DMAC),γ-butyrolactone, 1,2-dimethoxyethane (glyme),1-(2-methoxyethoxy)-2-methoxyethane (diglyme), 2,5,8,11-tetraoxadodecane(triglyme), dioxane, sulfolane, nitrobenzene and benzonitrile aresuitable, illustrative aprotic polar solvents for the preparation ofpolyfluoroalkoxides and their subsequent reaction with thepolyfluoroallyl chloride, bromide or fluorosulfate. DMF, diglyme,triglyme and acetonitrile are preferred solvents for these reactions.

The apparatus, reactants and solvents should be adequately dried for usein the process of the invention because the presence of water hydrolyzespolyfluoroalkoxides:

    (R.sub.F).sub.2 CFO.sup.- +H.sub.2 O→(R.sub.F).sub.2 C(OH.sub.2)+F.sup.-

    R.sub.F CF.sub.2 O.sup.- +H.sub.2 O→R.sub.F CO.sub.2 H+HF.sub.2.sup.-

Metal fluorides which are useful in this invention are potassiumfluoride (KF), rubidium fluoride (RbF), cesium fluoride (CsF) andtetraalkylammonium fluorides (R₄ NF) such as tetraethylammonium fluoride((C₂ H₅)₄ NF) and tetrabutylammonium fluoride (C₄ H₉)₄ NF). R, alike ordifferent, is alkyl of 1 to 6 carbon atoms, preferably 1 to 4 carbonatoms. Potassium fluoride is preferred because of its availability,economic advantage, and ease of handling.

Polyfluorinated carbonyl compounds which are useful in this inventionare ketones and carboxylic acid fluorides. Ketones give branchedfluorocarbon products, whereas acid fluorides give primary fluorocarbonproducts in which the new ether linkage is at the primary or secondarycenter: ##STR26##

Polyfluorinated ketones which are useful include hexafluoroacetone,chloropentafluoroacetone, 1,3-dichlorotetrafluoroacetone,1,1-difluoroethyl 2-oxopentafluoropropanesulfonate,dimethyltetrafluoroacetone-1,3-dicarboxylate,1,3-bis(2-heptafluoropropoxy)tetrafluoropropanone, octafluorobutanone,decafluoro-2-pentanone, dodecalfluoro-2-hexanone,tetradecafluoro-2-heptanone, hexadecafluoro-2-octanone,octadecafluoro-2-nonanone, eicosafluoro-2-decanone, and3-ketotetrafluoroglutaroyl fluoride.

Polyfluorinated acid fluorides which are useful include carbonylfluoride, trifluoroacetyl fluoride, pentafluoropropionyl fluoride,heptafluorobutyroyl fluoride, nonafluoropentanoyl fluoride ##STR27##undecafluorohexanoyl fluoride, tridecafluoroheptanoyl fluoride,pentadecafluorooctanoyl fluoride, heptadecafluorononanoyl fluoride,nonadecafluorodecanoyl fluoride, difluoromalonyl difluoride,tetrafluorosuccinyl difluoride, hexafluoropropane-1,3-dioyl difluoride(hexafluoroglutaryl difluoride), octafluorobutane-1,4-dioyl difluoride(octafluorodipoyl difluoride), decafluoropentane-1,5-dioyl difluoride(decafluoropimelyl difluoride), dodecafluorohexane-1,6-dioyl difluoride(dodecafluorosuberyl difluoride), fluorosulfonyldifluoroacetyl fluoride,2-(fluorosulfonyl)tetrafluoropropionyl fluoride,2-(heptafluoropropoxy)tetrafluoropropionyl fluoride,2-[2-(1-heptafluoropropoxy) hexafluoropropoxy]tetrafluoropropionylfluoride,2-{2-[2-(1-heptafluoropropoxy)hexafluoropropoxy]hexafluoropropoxy}tetrafluoropropionylfluoride, ##STR28## carbomethoxydifluoroacetyl fluoride,cyanodifluoroacetyl fluoride,5-carbomethoxyperfluoro(2-methyl-3-oxavaleroyl)fluoride and2-(pentafluorophenoxy)tetrafluoropropionyl fluoride.

The ketone 1,1-difluoroethyl 2-oxopentafluoropropanesulfonate (Example3) is a special case as a starting material because it is an in situsource of 2-oxopentafluoropropanesulfonyl fluoride since the latter hasnot been isolated. ##STR29##

Many of the above starting materials are commercially available, e.g.,PCR, Gainesville, Fla., is a supplier of fluorinated ketones andcarboxylic acids. Examples 2, 3, 4, 5, 7, 9, 10, 11, 12, 13, 16, 19, 23and 24 give sources and methods of preparation of some compounds whichare not commercially available. Generally, perfluoroketones can beprepared from the esters of perfluoroalkanecarboxylic acids and from thereaction of carbonyl fluoride with perfluoroalkenes (W. A. Sheppard andC. M. Sharts, "Organic Fluorine Chemistry", p. 365-368, W. A. Benjamin,New York, 1969, H. P. Braendlin and E. T. McBee, Advances in FluorineChemistry, 3, 1 (1963)). Perfluoroalkanecarboxylic acid fluorides andperfluoroalkane-α,ω-dicarboxylic acid difluorides are prepared bytreatment of the corresponding acids with sulfur tetrafluoride, by theaddition of carbonyl fluoride to perfluoroalkenes (F. S. Fawcett, C. W.Tullock and D. D. Coffman, J. Amer. Chem. Soc., 84 4275, 4285 (1962))and by electrolysis of alkanecarboxylic acids in hydrogen fluoride (M.Hudlicky, "Chemistry of Fluorine Compounds", p. 86, MacMillan Co., NewYork, 1962). Perfluoroalkanedicarboxylic acids are prepared by oxidationof fluorinated α,ω-dialkenes or fluorinated cycloalkenes (Hudlicky, loc.cit., p. 150-152). Perfluoroalkyl polyethers with a terminal acidfluoride group can be made from hexafluoropropene oxide and its fluorideion induced oligomers, as described by R. A. Darby, U.S. Patent3,450,684 (1969) and by P. Tarrant, C. G. Allison, K. P. Barthold and E.C. Stump, Jr., Fluorine Chem. Rev., 5, 88 (1971).

The stoichiometry of the displacement with polyfluoroallyl chloride,bromide or fluorosulfate requires one molar equivalent of this reagentfor each reactive center in the polyfluoroalkoxide anion. With adifunctional polyfluoroalkoxide, however, the stoichiometry can beadjusted to give either the mono- or the di-substitution product, thus:##STR30##

The formation of the polyfluoroalkoxide and its subsequent reaction withthe polyfluoroallyl chloride, bromide or fluorosulfate can be carriedout sequentially without isolation of intermediates in glass apparatusat atmospheric pressure using the normal precautions to excludemoisture. The use of cooling baths and low temperature condensers (e.g.those packed with dry ice and acetone mixtures) serves to moderate thereactions and facilitate the retention of volatile reagents andproducts. The progress of the displacement reaction is convenientlyfollowed by the appearance of a precipitate of the salt MZ (5), by gasliquid partition chromatography (glpc) and by fluorine nuclear magneticresonance spectroscopy (¹⁹ F NMR).

The displacement reaction can be carried out between -20° C. and +80°C., and is preferably between 0° C. and 30° C. Typically, the reactionmixture is cooled externally at 0° C. to 15° C. during the addition ofthe polyfluoroallyl chloride, bromide or fluorosulfate, and is thenallowed to warm up to 25° C. to 30° C. for the remainder of the reactiontime.

The time required to complete the displacement reaction varies from oneto 24 hours, and is preferably from 2 to 4 hours. Typically, thereaction mixture is externally cooled for 5 to 45 min while thepolyfluoroallyl chloride, bromide or fluorosulfate is being added, andis then stirred at room temperature for 2 to 3 hours.

The products of the reaction are isolated by standard procedures. Insome cases, the reaction product is appreciably more volatile than thehigh-boiling solvent used (diglyme bp 162° C., DMF bp 153° C.) and canbe distilled into a trap cooled to -80° C. by warming the reactionvessel to 30° C. to 50° C. under a reduced pressure of 1 to 200 mm ofHg. Alternatively, the reaction mixture can be poured into five to tentimes its volume of water; the insoluble lower layer of fluorinatedproduct is separated, washed free of solvent with more water, dried andfractionally distilled from phosphorus pentoxide or concentratedsulfuric acid.

The polyfluoroallyloxy compounds of this invention are unsaturatedmonomers which can be converted to new and useful polymers.Polyfluoroallyloxy monomers can be homopolymerized under high pressureto oligomeric compositions of matter. The economic factors of a costlymonomer and the necessity for high pressure operation, however, make itpreferable to incorporate these monomers into copolymers formed withless expensive ethylenically unsaturated monomers, e.g., olefins such asethylene and halogenated olefins such as tetrafluoroethylene,trifluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, andprovided tetrafluoroethylene or vinylidene fluoride is also presentperfluoro(methyl vinyl ether), perfluoro(propyl vinyl ether), andhexafluoropropylene. Halogenated olefins are preferred, especiallytetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, andmixtures of tetrafluoroethylene with perfluoro(methyl vinyl ether),perfluoro(propyl vinyl ether) or hexafluoropropylene. Such copolymershave either more desirable or entirely new properties not possessed bye.g., poly(tetrafluoroethylene), poly(trifluoroethylene),poly(vinylidene fluoride), poly(chlorotrifluoroethylene) orpolyethylene. Copolymerization may be defined as any process whereby twoor more monomers are incorporated as integral parts of a high polymer. Acopolymer is the product resulting from such a process. It is notnecessary that the relative numbers of the different types of unit bethe same in different molecules of the copolymer or even in differentportions of a single molecule.

Copolymers which contain from about 5-55 weight percent (about 1-25 molepercent) of polyfluoroallyloxy comonomer have lower melting points thanthe corresponding polyfluoroolefins, and consequently are more readilymolded and shaped into useful objects. Copolymers which contain fromabout 0.1-10 weight percent, preferably about 1-10 percent (about 0.3-5mole percent) of a polyfluoroallyloxy comonomer with pendant --SO₂ F or--COF groups can be partially hydrolyzed to a copolymer bearing --SO₂ OHor --CO₂ H groups which have an affinity for cationic dye molecules.Thus, it is possible to dye fluorocarbon polymers in a variety ofcolors. This cannot be done with polyfluoroolefins which do not haveincorporated comonomer of this type. Copolymers which contain from about5 to 35 weight percent (about 1.0 to 10 mole percent) of apolyfluoroallyloxy comonomer with pendant --SO₂ F, --OC₆ F₅, or --COFgroups can also be partially or essentially completely hydrolyzed to acopolymer bearing hydrophilic --SO₂ OH, --OC₆ F₄ OH and --CO₂ H groups.Such a copolymer has an affinity for water and is water-wettable.Polyfluoroolefins which do not have incorporated a comonomer of thistype are not wetted and are impermeable to water. A second importantfeature of copolymers which contain about 1.0 to 10 mole percent of apolyfluoroallyloxy comonomer bearing --SO₂ OH or --CO₂ H groups orionized forms thereof, e.g., --S0₂ O⁻ Na⁺ or --CO₂ ⁻ Na⁺, is theircapacity for ion exchange. A specific use for such polymers is in achloroalkali cell, such as disclosed in German Patent Application No.2,251,660, published April 26, 1973, and Netherlands Patent ApplicationNo. 72.17598, published June 29, 1973, wherein an ion-exchange polymerin the form of a film membrane or diaphragm is used to separate theanode and cathode portion of the cell from which chlorine and sodiumhydroxide are respectively produced from brine flowing within the anodeportion of the cell.

Copolymers which contain from about 0.1-10 weight percent of apolyfluoroallyloxy comonomer having pendant --CN groups are useful forimparting cure sites in fluoroelastomer compositions.

The properties of each copolymer depend upon the distribution of monomerunits along the polymer chain since a copolymer is not a physicalmixture of two or more polymers each derived from the respectivemonomers but a new material incorporating each monomer. It is well knownthat the composition of such a copolymer may also be quite differentfrom that of the monomer mixture (feed) from which it is formed.Furthermore, "the relative tendencies of monomers to be incorporatedinto polymer chains do not correspond at all to their relative rates ofpolymerization alone . . . the reactive properties of a growing polymerchain depend primarily upon the monomer unit at the growing end, and notupon the length and composition of the chain as a whole.", C. Walling,"Free Radicals In Solution", pages 99-100, John Wiley & Sons, Inc., NewYork (1957).

The copolymerization reaction to prepare the present copolymers can becarried out either in a nonaqueous or an aqueous medium with thereactants and initiator in solution, suspension, or emulsion form in aclosed vessel with agitation. This type of reaction is well known tothose skilled in the art.

The copolymerization is initiated by a free radical type initiator whichis generally present at a concentration of from 0.001 to 5 percent byweight of the reaction mixture, and is preferably from 0.01 to 1.0percent by weight. Such free radical initiator systems are preferablyoperable at or below 25° C., and are exemplified by, but not restrictedto pentafluoropropionyl peroxide (C₂ F₅ COO)₂, dinitrogen difluoride (N₂F₂), azobisisobutyronitrile, ultraviolet irradiation and ammonium orpotassium persulfate; mixtures of iron (II) sulfate with hydrogenperoxide, ammonium or potassium persulfate, cumene hydroperoxide,t-butyl hydroperoxide; mixtures of silver nitrate and ammonium orpotassium persulfate; mixtures of trifluoroacetic acid,pentafluoropropionic acid, heptafluorobutyric acid orpentadecafluorooctanoic acid with ammonium or potassium persulfate. Theperoxide systems may contain additionally sodium sulfite, sodiummetabisulfite, or sodium thiosulfate.

When aqueous emulsion systems are used for copolymerization they containemulsifying agents in the form of the sodium or potassium salts ofsaturated aliphatic acids of between about 14 and 20 carbon atoms or ofperfluoroalkanoic acids and perfluoroalkanesulfonic acids of between 6and 20 carbon atoms, e.g., potassium stearate or potassiumpentadecafluorooctanoate. These emulsifiers may constitute between 0.1and 10.0 weight percent of the reaction mixture and preferablyconstitute between 0.5 and 5 parts by weight percent.

Aqueous emulsion systems are customarily buffered to pH 7 or above bythe addition of reagents such as disodium hydrogen phosphate, sodiummetaborate, or ammonium metaborate to the amount of about 1 to 4 weightpercent of the reaction mixture.

The following three types of copolymerization systems are preferred inpreparing the preferred copolymers of this invention:

(1) Solutions of two or more comonomers in1,1,2-trichloro-1,2,2-trifluoroethane (Freon® 113) solvent containingpentafluoropropionyl peroxide are shaken in an autoclave at about 25° C.for about 20 hours. The crude polymer is isolated by evaporation of thesolvent and freed from monomers and lower oligomers by washing with moresolvent.

(2) An aqueous emulsion of two or more comonomers containing anemulsifier such as potassium perfluorooctanesulfonate and an initiatorsuch as ammonium persulfate is shaken in an autoclave at about 700° C.and internal pressures of 30-200 p.s.i.g. for 0.75 to 8 hours. Thepolymer is isolated by filtration or centrifugation.

(3) The polyfluoroallyloxy comonomer may be used as the solvent in placeof 1,1,2-trichloro-1,2,2-trifluoroethane in method (1) when it isdesired to incorporate a large proportion (up to 25 mole percent) of thepolyfluoroallyloxy component in the polymer.

SPECIFIC EMBODIMENTS OF THE INVENTION

The following illustrative examples demonstrate ways of carrying out theinvention. All parts and percentages are by weight unless otherwisestated. For structure confirmation analyses, fluorine nuclear magneticresonance chemical shifts are in parts per million from internalfluorotrichloromethane, and proton nuclear magnetic resonance chemicalshifts are in parts per million from internal tetramethylsilane.Infrared and nuclear magnetic resonance spectra were recorded onundiluted liquid samples unless otherwise stated.

EXAMPLE 11-(Heptafluoro-2-propoxy)-1,1,3,3,-tetrafluoro-2-chloro-2-propene

    (CF.sub.3).sub.2 CO+KF+CF.sub.2 ═CClCF.sub.2 Cl→(CF.sub.3).sub.2 CFOCF.sub.2 CCl═CF.sub.2

Hexafluoroacetone (16.6 g, 0.10 mol) was distilled into a stirredmixture of potassium fluoride (5.80 g, 0.10 mol) and1-(2-methoxyethoxy)-2-methoxyethane (hereinafter referred to as diglyme)(100 ml) to give a homogeneous solution. This mixture was maintained at25°-30° C. and treated with 1,2-dichloro-1,1,3,3,-tetrafluoropropene(18.3 g, 0.10 mol, prepared according to J. E. Bissey, H. Goldwhite andD. G. Rowsell, J. Org. Chem., 32, 1542 (1967)). The mixture was stirredovernight and then it was poured into water (500 ml). The lower layerwas washed with water (250 ml), dried, and distilled to give1-(heptafluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloropropene (13.0 g,0.039 mol, 39%), bp 82°-83° C. whose structure was confirmed by thefollowing: λ_(max) 5.72 (CCl═CF₂) and 7.5-10 μm (CF, C-O); ¹⁹ F NMR,-64.9 (m) 2F, -- OCF₂ C═C; -76.0 (2nd order m) 2F, C═CF₂ ; -81.2 (tJ=5.7 Hz, each member d J=2.2 Hz) 6F, CF₃ ; and -146.7 ppm (t J=22.9 Hzeach member septet J=2.2 Hz) 1F, CFO.

Anal. Calcd for C₆ ClF₁₁ O: C, 21.67; Cl, 10.66. Found: C, 21.43; Cl,10.89.

EXAMPLE 21-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-propene A.Pentafluoro-2-propenyl fluorosulfate (Perfluoroallyl fluorosulfate)##STR31##

A mixture of commercial liquid sulfur trioxide (10 ml) andhexafluoropropene (45 g, 0.30 mol) was sealed in a Carius tube at liquidnitrogen temperature, mixed well at 25° C., allowed to stand for 4 daysat 25° C., and finally heated in a steam bath for 6 hours. From two suchtubes, there was obtained by distillation,3-(trifluoromethyl)-3,4,4-trifluoro-1-oxa-2-thiacyclobutane 2,2-dioxide(2-hydroxy-1-trifluoromethyl-1,2,2,-trifluoroethane sulfonic acidsultone, D. C. England, M. A. Dietrich and R. V. Lindsey, Jr., J. Amer.Chem. Soc., 82 6181 (1960)) (25 g, 22%) bp 44° C., andpentafluoro-2-propenyl fluorosulfate (hereinafter referred to asperfluoroallyl fluorosulfate) (73 g, 63%), bp 58°-60° C.

Perfluoroallyl fluorosulfate is characterized by: λ_(max) 5.55 (C═C) and6.75 μm (SO₂); ¹⁹ F NMR, 46.1 (t J=8.5 Hz, each member d J=1.8 Hz) 1F,SO₂ F, -74.0 (d J=28.2 Hz, each member d J=13.9 Hz, d J=8.5 Hz, d J=7.8Hz) 2F, -91.2 (d J=50 Hz, each member d J=40.5 Hz, t J=7.8 Hz) 1F,-104.7 (d J=119.4 Hz, each member d J=50 Hz, d J=28.2 Hz) 1F, and -192.4ppm (d J=119.4 Hz, each member d J=40.5 Hz, t J=13.9 Hz, d J=1.8 Hz) 1F.

B. 1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-propene##STR32##

A suspension of potassium fluoride (5.80 g, 0.10 mol) and diglyme (100ml) was stirred at 20° C. in a cooling bath whilechloropentafluoroacetone (18.3 g, 0.10 mol) was distilled in. After thepotassium fluoride had dissolved, perfluoroallyl fluorosulfate (23.0 g,0.10 mol) was added rapidly with cooling of the reaction mixture. Theresulting exothermic reaction was accompanied by the precipitation ofsolid. The mixture was stirred at 25° C. for one hour, and then thevolatile components were transferred to a trap cooled to -80° C. byheating the reaction mixture at 42° C. (5 mm Hg). The volatile productwas distilled from phosphorus pentoxide to give1-(1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy)-pentafluoro-2-propene,(19.6 g, 0.059 mol, 59%) bp 85°-86° C. which was characterized by:λ_(max) 5.55 (CF═CF₂) and 7-10 μm (CF, C--O); ¹⁹ F NMR, -68.6 (m) 2F,CF₂ Cl, -69.1 (m) 2F, CF₂ O, -78.8 (m) 3F, CF₃, -93.2 (d J=54.7 Hz, eachmember d J=39.8 Hz, t J=7.5 Hz), 1F, cis-CF₂ --CF═CF, -105.9 (d J=116.7Hz, each member, d J=54.7 Hz, t J=24.0 Hz) 1F, trans--CF₂ --CF═CF,-141.2 (t J=22.8 Hz, each member m) 1F, CF, and -190.4 ppm (d J=116.7Hz, each member d J=39.8 Hz, t J=13.4 Hz) 1F, --CF₂ CF═C.

Anal. Calcd for C₆ ClF₁₁ O: C, 21.67; Cl, 10.66. Found: C, 21.34; Cl,10.21.

EXAMPLE 3 2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonylfluoride (2-Perfluoroallyloxypropane-1-sulfonyl fluoride) A.2-Oxopentafluoropropanesulfonic Acid ##STR33##

(i) Dropwise addition of sulfur trioxide (12.8 g, 0.16 mol) to2-ethoxy-1,1,3,3,3-pentafluoropropene (D. W. Wiley and H. E. Simmons, J.Org. Chem., 29, 1876 (1964)) (29.0 g, 0.165 mol) produced an exothermicreaction. The black reaction mixture was distilled to give recovered2-ethoxy-1,1,3,3,3-pentafluoropropene (6.3 g, 0.036 mol, 22%, identifiedby ir) and ethyl 2-oxopentafluoropropanesulfonate (20.2 g, 0.078 mol,49% conversion and 63% yield) bp 47°-48° C. (12 mm Hg): λ_(max) 3.34 and3.41 (saturated CH), 5.60 (C═O), 7.09 (SO₂ O), and 7.6-8.5 μm (C--F,SO₂); ¹ H NMR, δ4.59 (q J=7.2 Hz) 2H, OCH₂ and 1.51 ppm (t J=7.2 Hz) 3H,CH₃ ; ¹⁹ F NMR, -75.0 (t J=8.3 Hz) 3F, CF₃, and -107.4 ppm (q J=8.3 Hz)2F, CF₂.

(ii) The above reaction was repeated at 0°-5° C. with sulfur trioxide(88 g, 1.1 mol) and 2-ethoxy-1,1,3,3,3-pentafluoropropene (176 g, 1.0mol). The colorless reaction mixture, which darkened on standingovernight, was distilled to give recovered2-ethoxy-1,1,3,3,3-pentafluoropropene (28.6 g, 0.16 mol, 16%) bp 46°-48°C., ethyl 2-oxopentafluoropropanesulfonate (145.1 g, 0.57 mol, 57%conversion and 68% yield) bp 48°-52° C. (12 mm Hg), and a higher boilingfraction composed mainly of 2-oxopentafluoropropanesulfonic acid. Thecrude acid was redistilled at 81°-82° C. (6.2 mm Hg), yield 35.6 g (0.16mol, 16% conversion and 19% yield) of pure acid: λ_(max) (CCl₄, CaF₂plates) 3.3 and 4.2 (broad) (SOH), 5.58 (C═O), 7.13 (SO₂ O) and 7.5-9 μm(CF, SO₂); ¹ H NMR δ10.2 ppm (s) SO₂ OH; ¹⁹ F NMR, -76.2 (t J=7.5 Hz)3F, CF₃, and - 108 ppm (q J=7.5 Hz) 2F, CF₂.

Anal. Calcd for C₃ HF₅ O₄ S: C, 15.80; H, 0.44: F, 41.65; S, 14.06.Found: C, 15.95; H, 0.55; F, 41.55; S, 13.89.

(iii) Ethyl 2-oxopentafluoropropanesulfonate (25.6 g, 0.10 mol) wasstirred at 25° C. and treated with trifluoroacetic acid (17.1 g, 0.15mol). The mixture was allowed to stand overnight, and then it was heatedto reflux (60° C.) in a spinning band still. Fractional distillation ofthe mixture at a pot temperature below 100° C. gave2-oxopentafluoropropanesulfonic acid (18.4 g, 0.081 mol, 81%) bp 73° C.(2.6 mm Hg).

B. 1,1-Difluoroethyl 2-oxopentafluoropropanesulfonate ##STR34##

A metal tube containing 2-oxopentafluoropropanesulfonic acid (23.8 g,0.10 mol) was cooled below -40° C. and vinylidene fluoride(1,1-difluoroethene) (13 g, 0.20 mol) was added. The mixture was shakenand warmed to 25° C. where it was kept for 4 hours. Distillation of theliquid product gave 20.4 g (0.07 mol, 70%) of 1,1-difluoroethyl2-oxopentafluoropropanesulfonate, bp 62°-63° C. (50 mm Hg): λ_(max)(CCl₄) 5.54 (C═O), 6.96 (SO₂ O) and 7.5-9 μm (CF, SO₂); ¹ H NMR, δ2.06ppm (t J=14.3 Hz) CH₃ ; ¹⁹ F NMR, -58.3 (q J=14.3 Hz, each member tJ=7.1 Hz) 2F, OCF₂, -75.0 (t J=8.0 Hz) 3F, CF₃ and -106.1 ppm (q J= 8.0Hz, each member t J=7.1 Hz) 2F, CF₂ SO₂.

Anal. Calcd for C₅ H₃ F₇ O₄ S: C, 20.56; H, 1.03; F, 45.52. Found: C,20.73; H, 1.03; F, 45.72.

A similar experiment on a 0.8-mol scale gave an 86% yield of product bp60° C. (50 mm Hg). This material was stored in polytetrafluoroethylenebottles to avoid degradation.

C. 2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride##STR35##

A suspension of dry potassium fluoride (5.80 g; 0.10 mol) in 2, 5, 8,11-tetraoxadodecane (triglyme) (100 ml) was stirred and cooled at 0° C.while 1,1-difluoroethyl 2-oxopentafluoropropanesulfonate prepared as inExample 3B (29.2 g, 0.10 mol) was added. When the potassium fluoride hadnearly all dissolved, perfluoroallyl fluorosulfate prepared as inExample 2A (23.0 g, 0.10 mol) was added at 0° C., and the resultingmixture was stirred at 20°-26° C. for 3 hours. Volatile components wereremoved by distillation at a flask temperature of 25° C. and 1 mm Hgpressure. The distillate was washed with cold dilute ammonium hydroxide,dried and distilled to give2-(1-pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride(13.0 g, 0.034 mol, 34%), bp 47°-48° C. (60 mm Hg) whose structure wasconfirmed by: λ_(max) 5.59 (CF═CF₂), 6.80 (SO₂ F) and 7.5-10 μm (C--F,C--O, SO₂); ¹⁹ F NMR, +45.4 (m) 1F, SO₂ F, -70.0 (m) 2F, OCF₂, -78.0(quintet J=10.7 Hz) 3F, CF₃, -91.5 (d J=51.5 Hz, each member d J=39.5Hz, t J=7.5 Hz) 1F, cis-CF₂ CF=CF, -104.8 (d J=117.0 Hz, each member dJ=51.5 Hz, t J=25.5 Hz) 1F, trans-CF₂ CF═CF, -107.0 and -108.4 (AB J=255Hz, each member q J=10.7 Hz, m) 2F, CF₂ SO₂ F, -138.7 (t J=20.2 Hz, eachmember m) 1F, CF, and -190.8 ppm (d J=117.0 Hz, each member d J=39.5 Hz,t J=13.0 Hz) 1F, CF₂ CF═C.

Anal. Calcd. for C₆ F₁₂ O₃ S: C, 18.96; F, 59.98; S, 8.43. Found: C,19.24; F, 60.06; S, 8.26.

In a similar reaction to Example 3C, it was shown by ir that the gasesgenerated were composed mainly of acetyl fluoride and small amounts ofhexafluoropropene and sulfuryl fluoride.

EXAMPLE 41-{1,3-bis(2-Heptafluoropropoxy)-2-pentafluoropropoxy}pentafluoro-2-propeneA. 1,3-bis(2-heptafluoropropoxy)tetrafluoropropanone ##STR36##

A mixture of dry potassium fluoride (21.0 g, 0.36 mol), dryN,N-dimethylformamide (DMF) (150 ml), hexafluoroacetone (59.8 g, 0.36mol) and 1,3-dichlorotetrafluoroacetone (35.8 g, 0.18 mol) was heated atreflux (40°-60° C.) for 3 days. Distillation into a trap cooled to -80°C. gave recovered hexafluoroacetone (16.5 ml, 46%) and a 63 g of liquidbp 30°-145° C. The higher-boiling material was redistilled from sulfuricacid to give 1,3-bis(2-heptafluoropropoxy)tetrafluoropropanone (18.7 g,0.037 mol, 21% conversion, 39% yield based on hexafluoroacetone), bp117°-118° C.: λ_(max) (CCl₄) 5.51 (C═O) and 7.5-9 μm (CF,C--O--C); MSm/e 479 (M-F)⁺, 313 (M-F-CF₃ COCF₃)⁺, 263 (M-F-CF₃ COCF₃ -CF₂)⁺, 235[(CF₃)₂ CFOCF₂ ]⁺, 169 (C₃ F₇)⁺, 147 (CF₃ COCF₂)⁺, 97 (CF₃ CO)⁺ and 69(CF₃)⁺ ; ¹⁹ F NMR, -75.0 (d J=21.5 Hz, each member septet J=5.5 Hz) 2F,OCF₂, -81.4 (m) 6F, CF₃, and -145.3 ppm (t J=21.5 Hz, each member septetJ=2.1 Hz)1F, CF.

Anal. Calcd for C₉ F₁₈ O₃ : C, 21.70; F, 68.66. Found: C, 21.60; F,68.59.

B.1-{1,3-bis(2-Heptafluoropropoxy)-2-pentafluoropropoxy}pentafluoro-2-propen##STR37##

A mixture of 1,3-bis(2-heptafluoropropoxy)tetrafluoropropanone (20.0 g,0.04 mol), diglyme (100 ml) and potassium fluoride (2.32 g, 0.04 mol)was stirred and warmed to 55° C. The two liquid phases and solidoriginally present became homogeneous and stayed so upon cooling.Perfluoroallyl fluorosulfate prepared as in Example 2A (10.0 g, 0.043mol) was added rapidly at 10° C. and the mixture was allowed to warm.The slight exothermic reaction was accompanied by precipitation of solidand the appearance of a second liquid phase. The mixture was stirred for2 hours and then poured into water (350 ml). The lower layer was washedwith water (75 ml), dried over phosphorus pentoxide and distilled togive1-{1,3-bis(2-heptafluoropropoxy)-2-pentafluoropropoxy}-pentafluoro-2-propene(16.1 g, 0.024 mol, 62%) bp 64°-67° C. (25 mm Hg) whose structure wasconfirmed by: λ_(max) 5.57 (CF₂ ═CF) and 7.5-9 μm (CF, C--O); ¹⁹ F NMR,-69.4 (m) 2F, OCF₂ C═C; -80.3 (broad) 4F, CFOCF₂ -81.5 (s) 12F, CF₃,-93.7 (d J=54.0 Hz, each member d J=39.6 Hz, t J=7.8 Hz) 1F, cis-CF₂--CF═CF, -106.3 (d J=117.4 Hz, each member d J=54.0 Hz, t J=23.7 Hz) 1F,trans-CF₂ CF═CF, -145.8 (m) 3F, OCF, and -190.9 ppm (d J=117.4 Hz, eachmember d J=39.6 Hz, t J=16.6 Hz) 1F, CF₂ CF═C.

Anal. Calcd for C₁₂ F₂₄ O₃ : C, 22.24; F, 70.35. Found: C, 22.66; F,70.27.

EXAMPLE 5 3-(1-Pentafluoro-2-propenyloxy)tetrafluoropropionyl fluorideA. Difluoromalonyl difluoride ##STR38##

3-Methoxytetrafluoropropionyl fluoride (F. S. Fawcett, C. W. Tullock andD. D. Coffman, J. Amer. Chem. Soc., 84, 4275 (1962)) (81 g, 0.45 mol)was slowly added to sulfur trioxide (80 g, 1.0 mol) at 40° C., and theproduct difluoromalonyl difluoride, bp -9° C., was continuously removedby distillation through a low temperature still, yield 58 g (0.40 mol,90%). The product structure was confirmed by: λ_(max) 1860 cm⁻¹ (COF),¹⁹ F NMR (no solvent), +17.1 ppm (t J=10 Hz) 2F, COF and -114.2 ppm (tJ=10 Hz) 2F, CF₂.

B. 3-(1-Pentafluoro-2-propenyloxy)tetrafluoropropionyl fluoride##STR39##

A mixture of dry potassium fluoride (7.5 g, 0.13 mol) and diglyme (100ml) was stirred at 10° C. and difluoromalonyl difluoride from part A(18.5 g, 0.13 mol) was distilled into it. After 20 min. the potassiumfluoride was nearly all dissolved, and perfluoroallyl fluorosulfateprepared as in Example 2A (29.9 g, 0.13 mol) was added dropwise at10°-15° C. The mixture was stirred for 3 hours, then the volatilecomponents were removed at a pot temperature of 32° C. and 4.8 mm Hgpressure. Fractionation of the distillate gave3-(1-pentafluoro-2-propenyloxy)tetrafluoropropionyl fluoride (14.9 g,0.051 mol, 39%) bp 70°-71° C. and a small amount of higher bp material.The product structure was confirmed by: λ_(max) 5.33 (COF), 5.60(CF═CF₂) and 7.5-10 μm (CF,C--O); ¹⁹ F NMR 23.7 (apparent quintet, J˜7.5Hz) 1F, COF, -71.9 (d J=24.6 Hz, each member t J=13.9 Hz, d J=13.9 Hz, dJ=7.4 Hz) 2F, OCF₂ C═C, -86.7 (m) 2F, CF₂ O, -91.6 (d J=51.8 Hz, eachmember d J=39.4 Hz, t J=7.4 Hz) 1F, cis-CF₂ CF═CF, -105.1 (d J=117.1 Hz,each member d J=51.8 Hz, t J=24.6 Hz) 1F, trans-CF₂ -CF═CF, -122.0 (dJ=8.2 Hz, each member t J=3.1 Hz) 2F, FCOCF₂, and -191.0 ppm (d, J=117.1Hz, each member d, J=39.4 Hz, t J=13.9 Hz, t J=1.6 Hz) 1F, CF₂ -CF═C.

Anal. Calcd for C₆ F₁₀ O₂ : C, 24.51. Found: C, 24.56.

EXAMPLE 6 Perfluoro-3,6-dioxanon-8-enoyl Fluoride A.Tetrafluorodigylcolyl Chloride ##STR40##

A mixture of 307.6 g (1.46 mol) of dichlorotetrafluorodihydrofuran,157.8 g (3.9 mol) of NaOH, 312 g (1.97 mol) of potassium permanganateand 1500 ml of water was refluxed for 17 hours. A brief (steam)distillation gave 10.6 g (3%) of recovered dihydrofuran. The reactionmixture was filtered and the filter cake triturated with 2×400 ml ofwater. The combined aqueous solutions were evaporated to 1500 ml,treated cold with 300 ml of conc. H₂ SO₄ and extracted continuously withether for a day. The extracts were evaporated until ether was no longerevolved at 25° C. (0.5 mm Hg). To the crude solid diacid, 279 g (up to93% yield), was added 5 g (0.06 mol) of pyridine and 416.5 g (3.5 mol)of thionyl chloride. Little gas evolution occurred at this stage, butconsiderable gas evolved as the mixture was stirred and warmed past 40°C. Evolved gases were passed through a 0° trap; after 4 hours at ca. 40°C., gassing slowed and trap contents (10 ml) were returned to the pot.The mixture was then refluxed, with occasional return of cold trapcontents to the reaction, until the head temperature reached 81° C. andno gas was being evolved. Fractionation afforded 215.2 g (61% fromdihydrofuran) of tetrafluorodigylcolyl chloride, bp 94°-97° C. Structurewas confirmed by NMR: ¹⁹ F-77.0 ppm (s, --CF₂ O--).

Tetrafluorodigycolyl chloride, bp 96.5° C., has previously been preparedby a different route by R. E. Banks, E. D. Burling, B. A. Dodd, and K.Mullen, J. Chem. Soc. (C), 1706 (1969).

B. Tetrafluorodigylcolyl Fluoride ##STR41##

Conversion of the diacid chloride to the corresponding fluoride, bp32°-33° C., was accomplished by a scale-up of the procedure of R. E.Banks, E. D. Burling, B. A. Dodd, and K. Mullen, J. Chem. Soc. (c), 1706(1969). A mixture of 215 g (0.885 mol) of tetrafluorodiglycolyldichloride, 140.5 g (3.35 mol) of NaF, and 1200 ml of anhydrousacetonitrile was stirred overnight, then distilled to give a fractioncollected at 35°-79° C. The distillate was treated with 20 g of NaF anddistilled to give 105 g of tetrafluorodiglycolyl difluoride, bp 32°-33°C. Addition of another 100 g (2.38 mol) of NaF to the reaction mixtureand slow distillation afforded another fraction, bp 35°-81° C. Treatmentwith 10 g of NaF and fractionation gave another 37.0 g of difluorideproduct, bp 32°-33° C., for a total of 142 g (76%).

C. Perfluoro-3,6-dioxanon-8-enoyl Fluoride ##STR42##

A mixture of 38.9 g (0.67 mol) of KF, 141.5 g (0.67 mol) oftetrafluorodiglycolyl difluoride, and 500 ml of dry diglyme was stirredfor 30 minutes at 5° C., during which time nearly all of the KFdissolved. Then 154.1 g (0.67 mole) of perfluoroallyl fluorosulfate wasadded rapidly at 5° C. and the mixture was stirred at 0°-5° C. for 3hours, at 25° C. for 2 hours, and allowed to stand overnight. Volatileswere evaporated to diglyme reflux at 38° C. (3 mm Hg). Distillation ofvolatiles from 20 g of NaF gave 28.2 g (20%) of recovered diacidfluoride, bp 32°-33° C., and 125.0 g (52%) of monoacid fluoride, almostall of it bp 93°-94° C. Structure was confirmed by:

ir (CCl₄): 5.30 (COF), 5.59 (C═C), 8-9μ (CF, C--O). NMR: F 13.3 (m, 1 F,COF), -72.0 (d of d of t of d, J_(FF) 25, 13, 13, 7.7 Hz, 2F, ═CFCF₂),-77.5 (t of d, J_(FF) 11.5, 2.7 Hz, 2 F, CF₂ CO₂ F), -88.8 (t, J_(FF)11.5 Hz, 2 F, CF₂ OCF₂ COF), -89.4 (t, J_(FF) 12.7 Hz, 2 F, ═CFCF₂OCF₂), -91.9 (d of d of t, J_(FF) 52.7, 39.3, 7.7 Hz, 1F, cis-CF₂CF═CF), -105.3 (d of d of t, J_(FF) 117.6, 52.7, 24.6 Hz, 1 F, trans-CF₂CF═CF), and -190.8 ppm (d of d of t of t, J_(FF) 117.6, 39.3, 13.7, 1.6Hz, 1 F, CF₂ CF═).

EXAMPLE 7 2-(1-Pentafluoro-2-propenyloxy)tetrafluoroethanesulfonylfluoride ##STR43##

A suspension of potassium fluoride (5.8 g, 0.10 mol) in diglyme (100 ml)was stirred and cooled while fluorosulfonyldifluoroacetyl fluoride (18.0g, 0.10 mol) (D. C. England, M. A. Dietrich and R. V. Lindsey, Jr., J.Amer. Chem. Soc., 82 6181 (1960)) was added rapidly. The mixture wasstirred for 15 min at 20°-30° C. during which time the potassiumfluoride dissolved, and then it was treated with perfluoroallylfluorosulfate prepared as in Example 2A (25.0 g, 0.11 mol) at 20°-25° C.over 5 min. The mixture was stirred for 2 hours, during which time solidprecipitated, and the temperature rose to 28° C. and fell again. Thevolatile components were transferred to a trap cooled to -80° C. bywarming the solution to reflux at 38° C. (5 mm Hg). The distillate wastreated with concentrated sulfuric acid (10 ml) to remove diglyme, thendistilled to give2-(1-pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride (19.9g, 0.06 mol, 60%) bp 55°-56° C. (150 mm Hg). The product structure wasconfirmed by: λ_(max) 5.53 (CF₂ ═CF), 6.79 (SO₂ F) and 7-10 μm(CF,C--O,SO₂); ¹⁹ F NMR, +44.9 (t J=6 Hz, each member t J=6 Hz) 1F,FSO₂, -71.8 (d J=25.3 Hz, each member t J=13.8 Hz, d J=13.8 Hz, d J=7.3Hz) 2F, OCF₂ C═C, -83.0 (m) 2F, CF₂ CF₂ O, -90.9 (d J=50.6 Hz, eachmember d J=39.5 Hz, t J=7.3 Hz) 1F, cis-CF₂ CF═CF, -104.5 (d J=117.6 Hz,each member d J=50.6 Hz, t J=25.3 Hz) 1F, trans-CF₂ CF═CF, -113.0 (dJ=5.6 Hz, each member t J=2.9 Hz) 2F, FSO₂ CF₂, and -190.9 ppm (dJ=117.6 Hz, each member d J=39.5 Hz, t J=13.8 Hz, t J=3.2 Hz) 1F, CF₂CF═C.

Anal. Calcd for C₅ F₁₀ O₃ S: C, 18.19; F, 57.55; S, 9.71. Found: C,18.35; F, 57.40; S, 9.69.

EXAMPLE 8 2-(1-Pentafluoro-2-propenyloxy)tetrafluoroethanesulfonylfluoride ##STR44##

The procedure of Example 7 was followed, substituting acetonitrile fordiglyme as the solvent. The acetonitrile was not rigorously purified,and the yields of2-(1-pentafluoro-2-propenyloxy)tetrafluoroethanesulfonyl fluoride, pb54°-55° C. (150 mm Hg) ranged from 40-50%.

EXAMPLE 9 1-[1-(Pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonylfluoride ##STR45##

A mixture of potassium fluoride (5.80 g, 0.10 mol) and diglyme (100 ml)was stirred at 10° C. while 2-fluorosulfonyltetrafluoropropionylfluoride (23.0 g, 0.10 mol) (D. C. England, M. A. Dietrich and R. V.Lindsey, Jr., J. Amer. Chem. Soc., 82 6181 (1960)) was added. Theresulting solution was treated at 10° C. with perfluoroallylfluorosulfate prepared as in Example 2A, and after the addition wascomplete, the mixture was stirred at 25° C. for 3 hours, then it waspoured into water (500 ml). The lower layer was washed with water (100ml), dried and distilled to give1-[1-(pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl fluoride(25.7 g, 0.068 mol, 68%) bp 50° C. (60 mm Hg), pure by gas liquidpartition chromatography (glpc). The product structure was confirmed by:λ_(max) 5.55 (CF═CF₂), 6.78 (SO₂ F) and 7.5-10 μm (CF,C--O,SO₂); ¹⁹ FNMR, 54.9 (d J=20.7 Hz, each member q of J=10.4 Hz, d J=3.6 Hz) 1F, SO₂F, -71.8 (d J=25.0 Hz, each member t J=13.8 Hz, d J=13.8 Hz, d J=7.4 Hz)2F, OCF₂ C═C, -72.1 (m) 3F, CF₃, -75.5 (m) 2F, CFCF₂ O, -91.0 (d J=50.7Hz, each member d J=39.4 Hz, t J=7.4 Hz) 1F, cis-CF₂ CF═CF, -104.6 (dJ=117.6 Hz, each member d J=50.7 Hz, t J=25.0 Hz) 1F, trans-CF₂ CF═CF,-166.4 (d J=14.6 Hz, each member q J=7.2 Hz, d J=3.6 Hz) 1F, CF, and-191.1 ppm (d J=117.6 Hz, each member d J=39.4 Hz, t J=13.8 Hz, t J=1.7Hz) 1F CF₂ CF═C.

Anal. Calcd for C₆ F₁₂ O₃ S: C, 18.96; F, 59.98; S, 8.44. Found: C,18.70; F, 60.09; S, 8.08.

EXAMPLE 10 Perfluoro(4-oxa-6-heptenenitrile) A.3-Methoxytetrafluoro-propionamide ##STR46##

A solution of 140 g (0.74 mol) of methyl 3-methoxytetrafluoropropionatein 100 ml of ether was treated at 0° with 15.3 g (0.90 mol) of NH₃. Theresulting viscous mixture was stirred at 25° overnight and evaporated todryness at 25° (10 mm). The crude residue was then recrystallized fromether/hexane to give 123.6 g (95%) of 3-methoxytetrafluoropropionamide,mp 78°-80°. An analytical sample was recrystallized from ether/hexane,mp 83°-85°. IR (KBr): 2.95, 3.02 and 3.10 (NH₂), 3.37 and 3.49 (sat'dCH), 5.92 (C═O), 6.19 (NH₂), 7.5-10μ (CF, C--O). NMR ((CD₃)₂ CO): ¹ H6.67 (broad, 2H, NH₂) and 3.66 ppm (s, 3H, OCH_(3l) ); ¹⁹ F -120.6 (t,J_(FF) 4.7 Hz, 2F, CF₂) and -121.8 ppm (t, J_(FF) 4.7 Hz, of d, J_(HF)2.1 Hz, 2F, CF₂).

Anal. Calcd. for C₄ H₅ F₄ NO₂ : C, 27.44; H, 2.88; N, 8.00. Found: C,27.74; H, 2.93; N, 7.99.

B. 3-methoxytetrafluoropropionitrile

    CH.sub.3 OCF.sub.2 CF.sub.2 CONH.sub.2 →CH.sub.3 OCF.sub.2 CF.sub.2 CN

A solution of 52.5 g (0.30 mol) of the amide from Part A in 200 ml ofdiglyme was stirred at -10° while 47.5 g (0.60 mol) of pyridine and 63.0g (0.30 mol) of trifluoroacetic anhydride were added. The cooling bathwas removed, and the mixture was stirred at ca 25° for 2 hr. Evaporationof volatiles to 40° (4.5 mm) gave 42.7 g of crude product, which wasdistilled to afford 36.5 g (77%) of 3-methoxytetrafluoropropionitrile,bp 53°. IR (neat): 3.36 and 3.48 (sat'd CH), 4.42 (CN), 8-10μ (CF,C--O). NMR: ¹ H 3.78 ppm (s, OCH₃); ¹⁹ F -93.2 (t, J_(FF) 6.3 Hz, 2F,CF₂) and -108.8 ppm (t, J_(FF) 6.3 Hz, 2F, CF₂).

Anal. Calcd. for C₄ H₃ F₄ NO: C, 30.59; H, 1.92; N, 8.92. Found: C,30.83; H, 1.94; N, 8.77.

C. Cyanodifluoroacetyl fluoride ##STR47##

When 55.5 g (0.69 mol) of SO₃ was added to 109 g (0.69 mol) of nitrileprepared as in Part B, a mild exothermic reaction ensued. The mixturewas stirred 2 hr, then heated at reflux (50°) for 4 hr, during whichtime the pot temperature rose from 73° to 91° and some volatiles werecollected in the -80° trap. Distillation gave 19.1 g (18% assuming pure)of recovered nitrile and 67.3 g (86%) of methyl fluorosulfate. The bathtemperature was taken ultimately to 170°. Considerable tarry residue and22 ml at -80° of volatile products were also formed. Distillation of thevolatiles gave 17 g (20% conversion) of cyanodifluoroacetyl fluoride, bp8°. IR (gas phase): 4.42 (CN), 5.27 (COF), 8-10μ (CF) with small amountsof SO₂ and an unknown impurity present. NMR: ¹⁹ F+16.7 (t, J_(FF) 11.0Hz, 1F, COF) and -98.0 ppm (d, J_(FF) 11.0 Hz, 2F, CF₂). Mass spec: m/c122.9926 (M⁺ ; calcd. for C F NO, 122.9932), 103.9939 (M⁺ -F; calcd. forC F NO, 103.9949), 75.9961 (CF CN⁺ ; calcd. for C F N, 75.9999).

D. Perfluoro(4-Oxa-6-heptenenitrile) ##STR48##

To a suspension of 9.0 g (0.156 mol) of flamedried KF in 200 ml of drydiglyme at -10° was added 16 g (0.13 mol) of cyanodifluoroacetylfluoride from part C. The mixture was stirred at 0° for 30 min, afterwhich it was homogeneous. Then 33.9 g (0.15 mol) of CF₂ ═CFCF₂ OSO₂ Fwas added at 0°, and the mixture was stirred at 0°-5° for 4 hr, then at25° for 1 hr. Volatiles were removed at 40° (5 mm) and fractionated togive 22.4 g (63%) of perfluoro(4-oxa-6-heptenenitrile), bp 66°-67°. IR(CCl₄): 4.31 (CN), 5.61 (CF═CF₂), 8-10μ (CF, C--O). NMR: ¹⁹ F -71.9 (dof d of t of d, J_(FF) 25.0, 13.6, 12.7, 7.3 L Hz, 2F, OCF₂ C═), -88.1(t of t of m, J_(FF) 12.7, 5.0 Hz, 2F, OCF₂ CF₂), -90.9 (d of d of t,J_(FF) 50.3, 39.1, 7.3 Hz, 1F, cis-CF₂ CF═CFF), -104.5 (d of d of t,J_(FF) 116.6, 50.3, 25.0, 1F, trans-CF₂ CF═CFF), -109.3 (t, J_(FF) 5.0Hz, 2F, CF₂ CN), and -190.9 ppm (d of d of t of m, J_(FF) 116.6, 39.1,13.6 Hz, 1F, CF₂ CF═).

Anal. Calcd. for C₆ F₉ NO: C, 26.39; N, 5.13. Found: C, 26.37; N, 5.31.

EXAMPLE 11 Methyl Perfluoro(5-methyl-4,7-dioxa-9-decenoate) ##STR49##

Condensation of 5-carbomethoxyperfluoro(2-methyl-3-oxavaleroyl) fluoridewith KF/CF₂ ═CFCF₂ OSO₂ F was demonstrated by adding 16.1 g (0.50 mol)of it to a suspension of 32.0 g (0.55 mol) of flame dried KF in 500 mlof dry diglyme stirred at 0°. The mixture was stirred at 0°-10° for 10min, after which most of the KF had dissolved. Then 126.5 g (0.55 mol)of CF₂ ═CFCF₂ OSO₂ F was added rapidly, and the mixture was stirred at5°-10° for 3 hour, then 1 hr at 25°. The reaction mixture was pouredinto 2 l. of water, and the lower layer was washed with water, extractedwith 25 ml of conc. H₂ SO₄, clarified with CaSO₄, filtered and distilledto give 63.7 g (27%) of methylperfluoro(5-methyl-4,7-dioxa-9-decenoate), bp 61°- 62° (10 mm). IR(neat): 3.31, 3.37, and 3.48 (sat'd CH), 5.58 (broad; C═O, CF═CF₂),7-10μ (CF, C--O). NMR: ¹ H 3.93 ppm (s, OCH₃); ¹⁹ F -72.0 (m, 2F, CF₂C═), -80.6 (m, 3F, CF₃), -83.4 (m, 2F, CF₂ O), -83.9 (m, 2F, CF₂ O),-91.9 (d of d of t, J_(FF) 52.7, 39.5, 7.4 Hz, 1F, cis-CF₂ CF═CFF),-105.2 (d of d of t, J_(FF) 117.3, 52.7, 25.0 Hz, 1F, trans-CF₂ CF═CFF),-122.0 (t, J_(FF) 3.1 Hz, 2F, CF₂ C═O), -145.9 (t, J_(FF) 20.5 Hz, of m,1F, CF) and -191.1 ppm (d of d of t, J_(FF) 117.3, 39.5, 13.9 Hz, 1F,CF₂ CF═CF₂).

Anal. Calcd. for C₁₀ H₃ F₁₅ O₄ : C, 25.44; H, 0.64. Found: C, 25.57; H,0.66.

EXAMPLE 12 A. Perfluoro(3-allyloxyglutaroyl)Fluoride andPerfluoro(3-keto-6-oxa-8-nonenoyl)fluoride ##STR50##

To a suspension of 29.0 g (0.50 mol) of flamedried KF in 600 ml ofdiglyme stirred at 0° was added 111.0 g (0.50 mol) of3-ketotetrafluoroglutaroylfluoride prepared by the action of SO₃ onbis(2-methoxytetrafluoroethyl)ketone. The mixture was stirred for 30 minat 0°-5°, when nearly all of the KF had dissolved. Then 115 g (0.50 mol)of perfluoroallyl fluorosulfate was added dropwise, and the mixture wasstirred at 0°-5° for 4 hr, warmed slowly to 25°, and volatiles removedto 40° (5 mm) in the pot. The volatiles, 135.2 g, were distilled to givefractions, bp 45°-61° (100 mm), 105.2 g (57% crude), of which 100 g hadbp 59°-61° (100 mm) and was indicated by gc to contain one majorcomponent and minor (0-15%) amounts of a second product. IR (CCl₄): 5.31(COF), 5.57 (CF═CF₂, C═O), 7.2-10μ (CF, C--O). For a late fraction, bp61° (100 mm), of nearly pure perfluoro(3-allyloxyglutaroyl)fluoride, NMR(CCl₄): ¹ H v. small amount diglyme impurity; ¹⁹ F 24.6 (m, 2F, COF),-68.5 (m, 2F, OCT₂ C═), -91.2 (d of d of t, J_(FF) 51.4, 39.5, 7.3 Hz1F, cis-CF₂ CF═CFF), -104.8 (d of d of t, J_(FF) 117.6, 51.4, 25.2 Hz,1F, trans-CF₂ CF═CFF), -116.1 (m, 4F, CF₂ C═O), -141.2 (m, 1F, CF), and-190.8 ppm (d of d of d of t, J_(FF) 117.6, 39.5, 13.5 Hz, 1F, CF₂ CF═).An earlier fraction contained 2% of a second fluorinated componentidentified as perfluoro(3-keto-6-oxa-8-nonenonyl)fluoride by ¹⁹ F NMR.

B. Dimethyl Perfluoro-3-allyloxyglutarate and MethylPerfluoro(3-keto-6-oxa-8-nonanoate) ##STR51##

Perfluoro(3-allyloxyglutaroyl)fluoride from Part A was easily convertedto its dimethyl ester by treatement at 25°-40° with a mixture ofmethanol and NaF. Filtration and distillation gave pure dimethylperfluoro(3-allyloxyglutarate), bp 77° (0.70 mm), identified bycomparison of its IR spectrum with that of an authentic sample, in 42%overall yield from 3-ketotetrafluoroglutaroyl fluoride. Since thecoproduct, methyl perfluoro-(3-keto-6-oxa-8-nonanoate), is considerablylower boiling, it was easily separated during the fractionation.

EXAMPLE 13 Perfluoro-1,6-bis(2-propenyloxy)hexane ##STR52##

A mixture of potassium fluoride (11.62 g, 0.20 mol), diglyme (200 ml)and octafluoroadipoyl difluoride (PCR 28.2 g, 0.096 mol) was stirred at5° C. for 1.5 hours. The mixture was kept at 5°-10° C. whileperfluoroallyl fluorosulfate prepared as in Example 2A (46.0 g, 0.20mol) was added dropwise. When the addition was complete, the mixture wasstirred at 5° C. for 30 min, then it was allowed to warm to 25° C. andthe stirring was continued for a further 3 hours. After having stoodovernight, the mixture was poured into water (1 l.); the lower layer waswashed with water (150 ml), dried and distilled to give two products.

The lower-boiling fraction was perfluoro-1,6-bis(2-propenyloxy)hexane(21.1 g, 0.0355 mole, 37%), bp 84°-86° C. (20 mm Hg) whose structure wasconfirmed by: λ_(max) 5.59 (CF═CF₂) and 7.2-9.5 μm (C--F, C--O): ¹⁹ FNMR, -72.1 (d J=25.7 Hz, each member t J=13.3 Hz, d J=13.3 Hz, t J=7.6Hz) 2F, OCF₂ C═C, -84.2 (m) 2F, CF₂ O, -92.3 (d J=52.7 Hz, each member dJ=39.5 Hz, t J=7.6 Hz) 1F, cis-CF₂ CF═CF, -105.5 (d J=117.8 Hz, eachmember d J=52.7 Hz, t J=--25.7 Hz) 1F, trans-CF₂ CF═CF, -122.9 (m), CF₂,-126.2 (m) 2F, CF₂, and -191.0 ppm (d J= 117.8 Hz, each member d J=39.5Hz, t J=13.8 Hz) 1F, CF₂ -CF═C.

Anal. Calcd for C₁₂ F₂₂ O₂ : C, 24.26; F, 70.35. Found: C, 24.43; F,70.38.

The higher boiling fraction was the 2:1 complex ofperfluoro-6-(2-propenyloxy)hexanoic acid with diglyme (7.9 g, 0.0155mol, 16%), bp 109°-110° C. (5 mm Hg), formed by hydrolysis ofperfluoro-6-(2-propenyloxy)hexanoyl fluoride in the aqueous diglyme washsolutions. This complex had λ_(max) 3-4 (OH, C--H), 5.59 (with shoulder,CF₂ ═CF, CO₂ H), and 7.2-9 μm (CF, C--O, CH); ¹ H NMR, δ 11.93 (s) 1H,CO₂ H, 3.75 (s) 4H, OCH₂, and 3.52 (s) 3H, OCH₃ ; ¹⁹ F NMR, -71.9 (dJ=25.1 Hz, each member t J=13.4 Hz, d J=13.4 Hz, d J=7.5 Hz) 2F, OCF₂C═C, -84.1 (m) 2F, CF₂ CF₂ O, -92.0 (d J=52.3 Hz, each member d J=39.3Hz, t J=7.4 Hz) 1F, cis-CF₂ CF═CF, -105.2 (d J=117.7 Hz, each member dJ=52.3 Hz, t J=25.1 Hz), 1F, trans-CF₂ CF═CF, -119.6 (t J=12.6 Hz, eachmember t J=3.2 Hz) 2F, CF₂, -122.6 (m) 2F, CF₂, -123.5 (m) 2F, CF₂,-126.1 (m) 2F, CF₂, and -190.9 ppm (d J=117.7 Hz, each member d J=39.3Hz, t, J=13.8 Hz, t J=1.8 Hz 1F, CF₂ CF═C.

EXAMPLE 14 Methyl Perfluoro-3,6-dioxanon-8-enoate ##STR53##

A suspension of 42 g (1.0 mol) of NaF in 100 ml of methanol was stirredat 5° C. while 114 g (0.317 mol) of acid fluoride was added rapidly.After addition had been completed, the mixture was stirred overnight at25° C., filtered and the solid rinsed with ether. Distillation afforded102.0 g (86%) of methyl perfluoro-3,6-dioxanon-8-enoate, bp 60°-61° C.(20 mm Hg), containing small amounts of impurities. Redistillation gavesomewhat more pure ester (1-2% impurities by gc), bp 61°-62° C. (20 mmHg). Structure was confirmed by Ir (neat): 3.32, 3.37, 3.49 (CH₃), 5.57(C═O), 8-9.5μ (CF, C--O). NMR: H 3.95 ppm (s) with small impurites at3.53 and 3.33 ppm; ¹⁹ F -72.0 (d of d of t of d, J_(FF) 24, 13, 13, 7.5Hz, 2 F, ═CFCF₂), -78.0 (t, J_(FF) 11.6 Hz, 2 F, CF₂ CO₂ CH₃), -89.0 (t,J_(FF) 11.6 Hz, 2 F, CF₂ OCF₂ CO₂ CH₃), -89.5 (t, J_(FF) 12.6 Hz, 2 F,═CFCF₂ OCF₂), -92.3 (d of d of t, J_(FF) 53.2, 39.2, 7.5 Hz, 1 F,cis-CF₂ CF═CF), -105.2 (d of d of t, J_(FF) 117.3, 53.2, 24.3 Hz, 1F,trans-CF₂ CF-CF), and - 190.8 ppm (d of d of t of t, J_(FF) 117.3, 39.2,14.0, 1.6 Hz, 1 F, CF₂ CF═).

Anal. Calcd. for C₈ H₃ F₁₁ O₄ : C, 25.82; H, 0.81; F, 56.17. Found: C,26.17; H, 0.66; F, 56.24.

EXAMPLE 15 Dimethyl Perfluoro-3-alloxyglutarate A.1,3,3,5-Tetramethoxyoctafluoropentane

The synthesis of bis(2-methoxytetrafluoroethyl)ketone from dimethylcarbonate tetrafluoroethylene, and sodium methoxide has been describedby D. W. Wiley (U.S. Pat. No. 2,988,537 (1961)). An extension of thissynthesis has given 1,3,3,5-tetramethoxyoctafluoropentane in a one-potreaction. ##STR54##

A mixture of 27.0 g (0.50 mol) of sodium methoxide, 56.0 g (0.62 mol) ofdimethyl carbonate, and 100 ml of dry tetrahydrofuran was agitated in a350 ml tube under 1-3 atm of tetrafluoroethylene. Tetrafluoroethylenewas pressured in as consumed until 110 g (1.1 mol) had been added. Themildly exothermic reaction kept the temperature near 35° C.; after theaddition, the reaction mixture was heated at 40° C. for 1 hour. Theviscous solution from this reaction was treated directly with 75.6 g(0.60 mol) of dimethyl sulfate at 40° C. for 15 hours. Filtration anddistillation afforded 87.6 g (52%) of1,3,3,5-tetramethoxyoctafluoropentane, bp 54° C. (0.3 mm Hg), n_(D) ²⁴1.3605, whose structure was confirmed by IR 3.29, 3.33, and 3.42 (satdCH) 8-9μ (CF, COC). Nmr (CCl₄) 'H δ 3.68 (s, 1, CF₂ OCH₃) and 3.57 (p,J_(HF) 1.3 Hz, 1, C (OCH₃)₂); ¹⁹ F -88.2 (m, l, CR₂ O) and -116.5 ppm(m, l, CF₂).

Anal. Calcd. for C₉ H₁₂ F₈ O₄ : C, 32.16; H, 3.60; F, 45.21. Found: C,32.57; H, 3.72; F, 44.61.

B. Dimethyl Tetrafluoroacetone-1,3-dicarboxylate ##STR55##

To 50 ml of conc. H₂ SO₄ was added dropwise 33.6 g (0.10 mol) of thetetraether. After the mildly exothermic reaction had subsided, themixture was heated at 70° C. (50 mm Hg) to remove volatiles and thendistilled at ca. 50° C. (1 mm Hg). The crude distillate was thenfractionated to afford 16.9 g (69%) of dimethyltetrafluoroacetone-1,3-dicarboxylate, bp 58° C. (2 mm), n_(D) ²² 1.3713.Structure was confirmed by Ir 3.28, 3.34 and 3.48 (satd CH), 5.57 (C═O)5.64 (sh-C═O), 8-9μ (CF, COC) Nmr (CCl₄) 'H δ 4.00 (s, OCH₃); ¹⁹ F -113ppm (s, CF₂).

Anal. Calcd. for C₇ H₆ F₄ O₅ : C, 34.16; H, 2.46; F, 30.88 mol wt, 246.Found: C, 34.18; H, 2.66; F, 30.95; mol wt, 246 (mass spec).

The same reaction on a 0.56 mole scale gave the diester in 82% yield.

C. Dimethyl Perfluoro-3-alloxyglutarate ##STR56##

To 27.3 g (0.18 mol) dry CsF in 100 ml diglyme was added 43.5 g (0.18mol) O═C(CF₂ COOCH₃)₂ at 5°-10° C. and stirred for 1 hour; 41.4 g (0.18mol) CF₂ ═CFCF₂ OSO₂ F was added at 5°-10° C. and the mixture wasstirred further for 3 hours. The reaction mixture was thrown into 1liter of H₂ O and the lower layer separated. This was washed twice withH₂ O. After treatment with 20 ml H₂ SO₄ at 0° C. and extraction withFreon® 113, the extract was distilled in a molecular still to give 4.54g (7.2% yield) of product, bp=51°-53° C. (0.1 mm). Structure wasconfirmed by ¹⁹ F nmr (F11): -68.48 ppm (OCF₂ CF═); -93.45 ppm cis-(CF═CFF); -105.91 ppm trans-(CF═CF); -117.10 ppm (CF₂ COOCH₃); -142.78 ppm(CF₂ CF₂ OCF═); -190.35 ppm (CF═CF₂). 'H nmr (F11/TMS): 3.96 (singlet,CH₃). Ir (neat): 3.37μ, 3.49μ (sat CH); 5.60 2 (>C═O, CF₂ ═CF); 8-10μ(CF, CO).

Anal. Calcd for C₁₀ F₁₀ H₆ O₅ : C, 30.32; F, 47.96; H, 1.33. Found: C,30.45; F, 48.10; H, 1.48.

EXAMPLE 16 Perfluoro-3-(2-propoxy-2-methylethoxy)propene ##STR57##

A mixture of potassium fluoride (6.96 g, 0.12 mol), diglyme (150 ml) and2-(1-heptafluoropropoxy)tetrafluoropropionyl fluoride (dimer ofhexafluoropropene oxide obtained by treatment with fluoride ion) (29.4g, 0.089 mol) was stirred at 5° C. for 1 hour. Perfluoroallylfluorosulfate prepared as in Example 2A (27.6 g, 0.12 mol) was addeddropwise at 5° C., then the mixture was stirred at 5° C. for 3 hours,and at 25° C. overnight. The reaction mixture was poured into water (1l.), the lower layer was separated and the volatile components wereremoved at 25° C. (0.5 mm Hg). Distillation of the volatile componentsfrom concentrated sulfuric acid gaveperfluoro-3-(2-propoxy-2-methylethoxy)propene (25.2 g, 0.052 mol, 59%),bp 62°-63° C. (100 mm Hg) whose structure was confirmed by: λ_(max) 5.57(CF═CF₂) and 7.5- 9 μm (C--F, C--O); ¹⁹ F NMR, -72.2 (d J=25.5 Hz, eachmember t J=13.3 Hz, d J=13.3 Hz, d J=7.4 Hz) 2F, OCF₂ C═C, -81.0 (m) 3F,CF₃, -82.3 (m) 5F, CF₃ +OCF₂, -84.1 (m) 2F, CF₂ O, -92.1 (d J=52.7 Hz,each member d J=39.7 Hz, t J=7.4 Hz) 1F, cis-CF₂ CF═CF, -105.5 (dJ=117.8 Hz, each member d J=52.7 Hz, t J=25.5 Hz), 1F, trans-CF₂ CF═CF,-130.4 (s) 2F, CF₂, -145.9 (m) 1F, CF, and -191.0 ppm (d J=117.8 Hz,each member d J=39.7 Hz, t J=13.6 Hz) 1F, CF₂ CF═C.

Anal. Calcd for C₉ H₁₈ O₂ : C, 22.42; F, 70.94. Found: C, 22.18; F,70.96.

EXAMPLE 17 Perfluoro-1,3-bis(2-propenyloxy)propane ##STR58##

A mixture of potassium fluoride (15.3 g, 0.26 mol), diglyme (200 ml) anddifluoromalonyl difluoride prepared as in Example 5A (17.3 g, 0.12 mol)was stirred at 5° C. for 15 min. Perfluoroallyl fluorosulfate (57.5 g,0.25 mol) was added at 5°-10° C. over a 45 min period, and the mixturewas stirred at 5° C. for an additional hour, then at 25° C. for 2 hours.The reaction mixture was poured into water (1 l.), the lower layer waswashed with water (100 ml), dried and distilled to giveperfluoro-1,3-bis (2-propenyloxy)propane (12.0 g, 0.027 mol, 23%) bp88°-90° C. (200 mm Hg) whose structure was confirmed by: λ_(max) 5.59(CF═CF₂) and 7.2-9.5 μm (C--F, C--O); ¹⁹ F NMR, -72.2 (m) 2F, OCF₂ C═C,-84.6 (m) 2F, CF₂ CF₂ O, -92.3 (d J=53.0 Hz, each member d J=39.5 Hz, tJ=7.2 Hz) 1F, cis-CF₂ CF═CF, -105.6 (d J=117.8 Hz, each member d J=53.0Hz, t J=25.2 Hz) 1F, trans-CF₂ CF═CF, -130.0 (s) 1F, CF₂ and -191.0 ppm(d J=117.8 Hz, each member d J=39.5 Hz, t J=13.5 Hz) 1F, CF₂ CF═C.

Anal. Calcd for C₉ F₁₆ O₂ : C, 24.34; F, 68.45. Found: C, 24.67; F,68.36.

EXAMPLE 18 Perfluoro-3-(butoxy)propene

    CF.sub.3 CF.sub.2 CF.sub.2 COF+KF+CF.sub.2 ═CFCF.sub.2 OSO.sub.2 F→CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 OCF.sub.2 CF═CF.sub.2

A mixture of dry potassium fluoride (7.50 g, 0.13 mol), diglyme (100 ml)and heptafluorobutyroyl fluoride (prepared from the acid by treatmentwith sulfur tetrafluoride) (28.1 g, 0.13 mol) was stirred at 5° C. for30 min. Perfluoroallyl fluorosulfate was added dropwise at 5° C., themixture was stirred at this temperature for 1 hour, then at 25° C. for 3hours. The volatile components were transferred by distillation at 40°C. (8 mm Hg), washed with water (100 ml), and distilled from a smallamount of concentrated sulfuric acid to give perfluoro-3-(butoxy)propene(30.3 g, 0.083 mol, 64%) bp 80°-84° C. whose structure was confirmed by:λ_(max) 5.57 (CF═CF₂) and 7.2-9.5 μm (C--F, C--0); ¹⁹ F NMR -72.1 (dJ=25.2 Hz, each member t J=13.5 Hz, d J=13.5 Hz, d J=7.4 Hz) 2F, OCF₂C═C, -82.1 (t J-8.1 Hz, each member m), 3F, CF₃, -84.5 (m) 2F, CF₂ O,-92.1 (d J=52.3 Hz, each member d J=39.4 Hz, t J=7.4 Hz) 1F, cis-CF₂CF═CF, -105.5 (d J=117.5 Hz, each member d J=52.3 Hz, t J=25.2 Hz) 1F,trans-CF₂ CF═CF, -127.3 (m) 4F, CF₂, and -191.0 ppm (d J=117.5 Hz, eachmember d J=39.4 Hz, t J=13.7 Hz, m) 1F, CF₂ CF ═C.

Anal. Calcd for C₇ F₁₄ O: C, 22.97; F, 72.66. Found: C, 23.20; F, 72.80.

EXAMPLE 19 Perfluoro-3-(octyloxy)propene

    F(CF.sub.2).sub.7 COF+KF+CF.sub.2 ═CFCF.sub.2 OSO.sub.2 F→F(CF.sub.2).sub.8 OCF.sub.2 CF═CF.sub.2

A mixture of potassium fluoride (5.80 g, 0.10 mol), diglyme (150 ml) andpentadecafluorooctanoyl fluoride (prepared by treating commercialperfluorooctanoic acid with sulfur tetrafluoride) (25.0 g, 0.06 mol) wasstirred at 5° C. for 1 hour. Perfluoroallyl fluorosulfate (23.0 g, 0.10mol) was added dropwise and the mixture was stirred at 5° C. for 4hours, then at 25° C. for an additional 3 hours. The mixture was pouredinto water (1 l.), separated, and the lower layer was distilled fromconcentrated sulfuric acid to give perfluoro-3-(octyloxy)propene (27.1g, 0.048 mol, 80%) bp 69°-70° C. (20 mm Hg) whose structure wasconfirmed by: λ_(max) 5.59 (CF═CF₂) and 8-9 μm (CF C--O); ¹⁹ F NMR -71.8(d J=25.1 Hz, each member d J=13.4 Hz, t J=13.4 Hz, d J=7.7 Hz) 2F, OCF₂C═C, -81.6 (t J=10.0 Hz) 3F, CF₃, -83.8 (m) 2F, CF₂ CF₂ O, -92.3 (dJ=53.6 Hz, each member d J=39.9 Hz, t J=7.7 Hz) 1F, cis-CF₂ CF═CF,-105.5 (d J=117.8 Hz, each member d J=53.5 Hz, t J=25.1 Hz) 1F,trans-CF₂ CF═CF, -122.2 (m) 6F, CF₂ , -122.9 (m) 2F, CF₂, -125.7 (m) 2F,CF₂, -126.5 (m) 2F, CF₂, and -190.8 ppm (d J=117.8 Hz, each member dJ=39.9 Hz, t 13.7 Hz, t 1.7 Hz) 1F, CF₂ CF═C.

Anal. Calcd for C₁₁ F₂₂ O: C, 23.34; F, 73.84. Found: C, 22.99; F,73.94.

EXAMPLE 20 2-Trifluoromethoxypentafluoropropene(Perfluoro(allylmethylether))

    COF.sub.2 +CsF+CF.sub.2 ═CFCF.sub.2 OSO.sub.2 F→CF.sub.3 OCF.sub.2 CF═CF.sub.2

A mixture of carbonyl fluoride (18.0 g, 0.27 mol), cesium fluoride (38.0g, 0.25 mol) and dry diglyme (300 ml) was stirred at -20° C. to -10° C.for 2 hours, then kept at -10° C. or below while perfluoroallylfluorosulfate (46.0 g, 0.20 mol) was added. The mixture was stirred at-10° C. for 2 hours, at 0° C. for 2 hours, then at 25° C. overnight. Themixture was warmed under a slight vacuum, and the volatile distillate(11 ml of liquid collected at -80° C.) was redistilled through a lowtemperature still to give 2-trifluoromethoxypropene (3.2 g, 2.0 ml at-80° C., 0.014 mol, 7%) bp 11°-12° C. The structure was established byits spectra: λ_(max) (gas phase) 5.55 (CF═CF₂), 8-9 (CF, C--O) and 5.35μm (weak COF impurity band); ¹⁹ F NMR (CCl₄), -56.5 (t J=9.2 Hz) 3F, CF₃O, -74.6 (d J=25.8 Hz, each member d J=13.6, q J=9.2 Hz, d J=7.1 Hz) 2F,OCF₂ C═C; -92.2 (d J=53.4 Hz, each member d J=39.2 Hz, t J=7.1 Hz) 1F,cis --CF₂ CF═CF, -105.5 (d J=118.0 Hz, each member d J=53.4 Hz, t J=25.8Hz), 1F, trans-CF₂ CF═CF, and -190.9 ppm (d J=118.0 Hz, each member dJ=39.2 Hz, t J=13.6 Hz) 1F, CF₂ CF═C.

EXAMPLE 21 Perfluoro-6-(2-propenyloxy)hexanoic Acid and Its Methyl Ester##STR59##

A mixture of potassium fluoride (11.7 g, 0.20 mol), diglyme (250 ml) andoctafluoroadipoyl difluoride (PCR 58.8 g, 0.20 mol) was stirred at 0°-5°C. for 30 min. The mixture was kept at 0°-5° C. while perfluoroallylfluorosulfate (Example 2A, 46.0 g, 0.20 mol) was added dropwise. Whenthe addition was complete, the mixture was stirred at 0°-5° C. for 2hours, then it was allowed to warm to 25° C. and the stirring wascontinued for a further 4 hours. Evacuation of the reaction mixture to35° C. (3 mm Hg) removed 45 ml of liquid. The higher boiling residue waspoured in water (1 l.); the lower layer (10 ml) was combined with thevolatile fraction from above and treated with a mixture of water (100ml) and diglyme (20 ml). After the resulting exothermic reaction, themixture was allowed to cool, and the lower layer was separated anddistilled to give perfluoro-1,6-bis(2-propenyloxy)hexane (Example 13,13.6 g, 0.023 mol, 23%) bp 61° (6 mm Hg) and the 2:1 complex ofperfluoro-6-(2-propenyloxy) hexanoic acid with diglyme (Example 13, 52.8g, 0.109 mol, 54.5%) bp 82°-84° C. (0.8 mm Hg).

The diglyme complex of the higher boiling fraction was distilled fromconcentrated sulfuric acid (40 ml) to giveperfluoro-6-(2-propenyloxy)hexanoic acid containing 12% of its methylester. The ester arises from the action of sulfuric acid on the diglymepresent in the complex. These products were identified by infraredλ_(max) 2.82 and 3-4 (OH,CH₃), 5.58 (CF═CF₂), 5.61 (C═O) and 7-10 μm(CF, C--O, CH) and by ¹ H NMR, δ 3.92 (OCH₃) and 11.33 ppm (OH) signalsin the ratio of 1:7.2; the ¹⁹ F NMR spectrum was also in accord withthese structures.

EXAMPLE 22 Perfluoro-6-(2-propenyloxy)hexanoic Acid

A reaction was carried out as described in Example 21. The crudereaction mixture was poured into water (750 ml), and the lower layer waswashed with water (100 ml). The same two products were obtained as inExample 21 by distillation of the crude lower layer. The fraction bp45°-53° C. (6 mm Hg) was freed of diglyme by water washing to leavecrude perfluoro-1, 6-bis(2-propenyloxy)hexane (9.5 g, 0.016 mol, 16%).

The higher boiling complex of perfluoro-6-(2-propenyloxy)hexanoic acidwith diglyme was dissolved in 1,1,2-trichloro-1,2,2-trifluoroethylene(50 ml) and extracted in turn with 50 ml and 25 ml of concentratedsulfuric acid. The organic layer was treated with calcium sulfate,filtered, and distilled to give pure perfluoro-6-(2-propenyloxy)hexanoicacid (42.2 g, 0.0988 mol, 49%) bp 75° C. (1.0 mm Hg). This material wasidentified by infrared λ_(max) 2.85-4.0 (H-bonded OH), 5.57 (CF═CF₂),5.63 (sh, C═O) and 8-9 μm (CF, C--O), and by its ¹ H and ¹⁹ F NMRspectra.

Anal. Calcd. for C₉ HF₁₅ O₃ : C, 24.45; H, 0.23; F, 64.66. Found: C,24.48; H, 0.45; F, 65.76.

EXAMPLE 23 Perfluoro(4,7-dioxa-6,9-dimethyl-9-propoxy)non-1;-ene##STR60##

A suspension of 58.1 g (1.0 mol) of flame-dried KF in 1400 ml of drydiglyme was stirred at 25° while 333 g (0.67 mol) of hexafluoropropeneoxide trimer was added rapidly. The two-phase system was stirred at 25°for 2 hr, during which time about half of the fluorocarbon layer slowlydissolved. The mixture was stirred at 5°-10° while 230 g (1.0 mol) of 1was added. The mixture was stirred at 5°-10° for 2.5 hr, then overnightat 25°, and poured into 2 l. of H₂ O. The aqueous layer was extractedwith 100 ml of CFCl₂ CF₂ Cl, and the combined organic layers washed with2 l. of H₂ O, extracted with 100 ml of conc. H₂ SO₄, clarified withCaSO₄, filtered and distilled. Hydrolysis and bubbling were apparent inthe water washed. Distillation afforded major fractions of 2 and 3, bp55°-71° (20 mm) and 140 g of crude CF₃ CF₂ CF₂ OCF(CF₃)CF₂ OCF(CF₃)CO₂H, bp mainly 101°-104° (20 mm). Redistillation of combined fractions of2 and 3 gave 80 g of impure 3, bp 81°-86° (80 mm) and 33.0 g (8%) of 2,bp 94°-95° (80 mm).

For 2, IR (neat): 5.59 (CF═CF₂), 7.5-9μ (CF, C--O). NMR: F -72.4 (d of dof t of d, J_(FF) 25.5, 13.2, ˜13, 7.0 Hz, 2F, OCF₂ C═), =80.9 (m, 8F,2CF₃ CF+CFCF₂ OCF), -82.4 (broad s, 5F, CF₃ CF₂ CF₂), -84.3 (broad, 2F,CFCF₂ OCF₂), -92.0 (d of d of t of d J_(FF) 52.1, 39.3, 7.0, 3.1 Hz, 1F,cis-CF═CFF), -105.5 (d of d of t, J_(FF) 117.9, 52.1, 25.5 Hz, 1F,trans-CF═CFF), -130.6 (s, 2F, CF₃ CF₂), -146.1 (m, 2F, CF), and -191.1ppm (d of d of t, J_(FF) 117.9, 39.3, 13.2 Hz, 1F, --CF═CF₂).

Anal. Calcd. for C₁₂ F₂₄ O₃ : C, 22.24; F, 70.36. Found: C, 22.50; F,71.78.

EXAMPLE 24 Perfluoro-6-phenoxy-4-oxa-1-Heptene ##STR61##

A suspension of 17.4 g (0.30 mol) of flame-dried KF in 500 ml of diglymewas stirred at 5° while 86.1 g (0.26 mol) ofperfluoro-2-phenoxypropionyl fluoride prepared by reaction of a metalsalt of pentafluorophenol with HFPO) was added dropwise. The mixture wasstirred for 30 min at 5°, after which the KF had partially dissolved.Then 69.0 g (0.30 mol) of perfluoroallyl fluorosulfate was addeddropwise, and the mixture was stirred at 5°-10° for 3 hr. The coolingbath was removed, and the mixture was stirred overnight. The reactionmixture was then drowned in 2 l. of water, and the lower layer waswashed with 1 l., then with 500 ml of water, dried over CaSO₄, filteredand distilled to afford 20.8 g (17%) ofperfluoro-6-phenoxy-4-oxa-1-heptene, bp 68°-75° (10 mm). A late fractionwas analyzed. IR (neat): 5.58 (CF═CF₂), 6.57 and 6.80 (arom. C═C), 7.5-9IR (neat): 5.58 (CF═CF₂), 6.57 and 6.80 (arom. C═C), 7.5-9∥ (CF, C-O)with a weak peak at 5.64 (--OCF═CFCF₃). NMR (CCl₄): ¹⁹ F -77.8 (d of dof t of d, J_(FF) 25.5, 13.7, ˜13, 7.2 Hz, 2F, OCF₂ C═), -79.8 (m, 3F,CF₃), -83.0 (m, 2F, CF₂ O), -91.7 (d of d of t, J_(FF) 52.0, 39.2, 7.2Hz, 1F, cis CF₂ CF═CFF), -105.1 (d of d of t, J_(FF) 118.0, 52.0, 25.5Hz, 1F, trans-CF₂ CF═CFF), -139.9 (t of m, J_(FF) 18.7 Hz, 1F, CF),-150.8 (m, 2F, arom. CF), -156.1 (t, J_(FF) 21.0 Hz, 1F, arom. CF),-162.3 (m, 2F, arom. CF), and -190.6 ppm (d of d of t of t, J_(FF)118.0, 39.2, 13.7, 1.6 Hz, 1F, CF₂ CF═). Impurity bands ascribable tothe isomer C₆ F₅ OCF(CF₃)CF₂ OCF═CFCF₃ were also present.

The following examples illustrate the preparation of useful copolymersfrom the polyfluoroallyloxy comonomers of this invention. The generalproperties of these copolymers were discussed above.

UTILITY EXAMPLES Example A Solution Polymerization ofTetrafluoroethylene with2-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride##STR62##

An 80-ml stainless steel-lined tube was charged with a cold mixture(-45° C.) of 1,1,2-trichloro-1,2,2-trifluoroethane (Freon® 113) (10 ml),8% 1,1,2-trichloro-1,2,2-trifluoroethane solution ofpentafluoropropionyl peroxide (3P initiator) (1 ml), and2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride(Example 7, 17.5 g, 0.053 mol). The tube was closed, cooled to -40° C.,evacuated, and charged with tetrafluoroethylene (20 g, 0.20 mol). Thetube was warmed to 25° C. and shaken at this temperature for 20 hours.The volatile materials were allowed to evaporate, and the productpolymer was evacuated to 0.5 mm Hg. The product was then extracted with1,1,2-trichloro-1,2,2-trifluoroethane, and dried under vacuum to givethe solid white copolymer (16.9 g, 85%): λ_(max) (KBr) 6.79 (So₂ F) and12.3 μm (broad) in addition to the usual polytetrafluoroethyleneinfrared bands. Gravimetric sulfur analysis gave 0.48 and 0.20% S,corresponding to an average of 0.34% S or 3.5 wt. % (1.1 mole %) ofpolyfluoroallyloxy comonomer corresponding to an equivalent weight of9400. Equivalent weight is the molecular weight of the polymer perfunctional group (here --SO₂ F). Differential scanning calorimetry (DSC)showed a 12% depression of the endotherm peak (mp) compared topolytetrafluoroethylene.

Example B Solution Polymerization of Tetrafluoroethylene with1-[1-(Pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl Fluoride##STR63##

The procedure of Example A was followed with1,1,2-trichloro-1,2,2-trifluoroethane (10 ml), 8% pentafluoropropionylperoxide in 1,1,2-trichloro-1,2,2-trifluoroethane (2.0 ml),1-[1-(pentafluoro-2-propenyloxy)]hexafluoropropane-2-sulfonyl fluoride(Example 9, 17.4 g, 0.046 mol) and tetrafluoroethylene (20 g, 0.20 mol)to give 16.7 g (79%) of copolymer. Analysis by X-ray fluorescence showed0.49% S present, corresponding to 5.8 wt-% (1.6 mole %) ofpolyfluoroallyloxy comonomer corresponding to an equivalent weight of6540. The sample had a mp depression of 11° C. compared topolytetrafluoroethylene by DSC.

Example C Solution Polymerization of Tetrafluoroethylene with3-[1-(Pentafluoro-2-propenyloxy)tetrafluoropropionyl Fluoride ##STR64##

The procedure of Example A was used with3-[-1(pentafluoro-2-propenyloxy)]tetrafluoropropionyl fluoride (Example5, 13.3 g, 0.045 mol) in place of2-[1-(pentafluoro-2-propenyloxy)]-tetrafluoroethanesulfonyl fluoride togive 17.8 g (86%) of copolymer: .sup.λ max (KBr) 5.62 (CO₂ H, weak) and9.7 μm bands in addition to the polytetrafluoroethylene bands; mpdepression (DSC) was 14° C. compared to polytetrafluoroethylene;gravimetric analysis showed 3.7 wt % of polyfluoroallyloxy comonomercorresponding to an equivalent weight of 7900.

A sample of the polymer was stirred with a solution of sodium hydroxidein 33% ethanol for 2 days, filtered, and washed with water until theextracts were no longer basic. The resulting polymer, now readily wettedby water, was dried under vacuum. Analysis by atomic absorptionspectroscopy showed 0.29% Na, corresponding to 3.7 wt-% (1.3 mole %) ofthe original comonomer.

Example D Solution Polymerization of Tetrafluoroethylene with1-(1,1,1,2,3,3-Hexafluoro-3-chloro-2-propoxy)pentafluoro-2-propene##STR65##

The procedure of Example A was used with1-(1,1,1,2,3,3-hexafluoro-3-chloro-2-propoxy)pentafluoro-2-propene(Example 2, 14.3 g, 0.043 mol) in place of2-[1-(pentafluoro-2-propenyloxy)]-tetrafluoroethanesulfonyl fluoride togive 18.3 g (87%) of copolymer: mp depression (DSC) 14° C. compared topolytetrafluoroethylene; gravimetric analysis gave 0.61 and 0.61% Cl,corresponding to 5.7 Wt-% of polyfluoroallyloxy comonomer and anequivalent weight of 5800; more accurate analysis by X-ray fluorescencegave 0.53% Cl corresponding to 5.0 wt-% (1.56 mole %) ofpolyfluoroallyloxy comonomer. The mp depression of 14° C. compared topolytetrafluoroethylene corresponds to a depression of 1° C. per 0.1 mol% of poly-fluoroallyloxy comonomer present. In contrast to this result,the smaller branch in hexafluoropropene gives a mp depressioncorresponding to about 1° C. per 0.3 mol-% of comonomer in its copolymerwith tetrafluoroethylene. This means that the copolymers prepared fromthe polyfluoroallyloxy comonomers have better molding properties for thesame mol-% incorporation of comonomer than those prepared fromhexafluoropropene comonomer.

Example E Solution Polymerization of Tetrafluoroethylene with2-(1-Pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl Fluoride##STR66##

The procedure of Example A was used with2-(1-pentafluoro-2-propenyloxy)hexafluoropropane-1-sulfonyl fluoride(Example 3, 16.1 g, 0.042 mol) in place of2-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride togive 18.5 g (88%) of copolymer: mp depression (DSC) 8° C. compared topolytetrafluoroethylene; analysis by X-ray fluorescence showed 0.43% S,corresponding to 5.1 wt-% (1.4 mole % ) of polyfluoroallyloxy conomomerand an equivalent weight of 7460.

Example F Solution Polymerization of Vinylidene Fluoride with2-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride

    CH.sub.2 ═CF.sub.2 +CF.sub.2 ═CFCF.sub.2 OCF.sub.2 CF.sub.2 SO.sub.2 F→Copolymer

The procedure of Example A was used with vinylidene fluoride (20 g, 0.32mol), 2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonylfluoride (Example 7, 16.5 g, 0.05 mol),1,1,2-trichloro-1,2,2-trifluoroethane (10 ml), and 8%1,1,2-trichloro-1,2,2-trifluoroethane solution of pentafluoropropionylperoxide (5 ml). The mixture was shaken overnight, the maximum recordedtemperature being 31° C. The solid copolymer produced (21.5 g, 60%)contained 46 wt % (14.2 mol %) of polyfluoroallyloxy comonomer with anequivalent weight of 71.9 DSC showed no thermal events between 25° C.and 400° C.

Anal. Calcd for (CH₂ ═CF₂)6.05 (CF₂ ═CFCF₂ OCF₂ CF₂ SO₂ F): C, 28.62; H,1.70; S, 4.7: Found: C, 28.49; H, 1.71; S, 4.46.

Example G Solution Polymerization of Vinylidene Fluoride with1-(Heptafluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloro-2-propene

    CH.sub.2 ═CF.sub.2 +CF.sub.2 ═CClCF.sub.2 OCF(CF.sub.3).sub.2 →Copolymer

The procedure of Example F was used with1-heptafluoro-2-propoxy)-1,1,3,3-tetrafluoro-2-chloro-2-propene (Example1, 10.5 g, 0.032 mol) in place of2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride togive a solid copolymer (20.6 g, 73%). This material contained 36 wt-%(9.8 mol-%) of polyfluoroallyloxy comonomer with an equivalent weight of878. DSC confirmed the structure as a copolymer and indicated itsstability, because no thermal events were observed in the range 25°-400°C.

Example H Solution Polymerization of Tetrafluoroethylene withPerfluoro-3-(butoxy)propene

    CF.sub.2 ═CF.sub.2 +CF.sub.3 (CF.sub.2).sub.3 OCF.sub.2 CF═CF.sub.2 →Copolymer

The procedure of Example A, when used with perfluoro-3-(butoxy)propene(Example 18, 19.0 g, 0.052 mol), tetrafluoroethylene (20 g, 0.20 mol),1,1,2-trichloro-1,2,2-trifluoroethane (10 ml) and 8%pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane(2 ml) gave 18.9 g of solid copolymer. This crude material was choppedin a blender with more solvent, rinsed, and dried to give 16.5 g ofcopolymer with a mp of 309° C., indicating that it was a true copolymer.

Example I Solution Polymerization of Tetrafluoroethylene withPerfluoro-1,6-bis(2-propenyloxy)hexane

    CF.sub.2 ═CF.sub.2 +(CF.sub.2 ═CFCF.sub.2 OCF.sub.2 CF.sub.2 CF.sub.2).sub.2 →Copolymer

The procedure of Example H was followed, usingperfluoro-1,6-bis(2-propenyloxy)hexane (Example 13, 20 g, 0.20 mol) forthe polyfluoroallyloxy comonomer. This gave 16.3 g of dry pulverizedpolymer with λ_(max) 5.55 μm (CF═CF₂); the remainder of the infraredspectrum resembled that of poly(tetrafluoroethylene). DSC showed apronounced exotherm Tp 315° C. followed by the endotherm Tp˜333° C. and339° C. on the first heating; the second heating showed no exotherm anda broad endotherm Tp˜326° C. Infrared spectra indicated that pyrolyticreactions of pendant pentafluoroallyloxy groups had occurred during thefirst heating; the broad DSC endotherm near the normally sharp mp ofpoly(tetrafluoroethylene) indicates that crosslinking had occurred.

Example J Solution Polymerization of Vinylidene Fluoride andPerfluoro-1,3-bis(2-propenyloxy)propane

    CH.sub.2 ═CF.sub.2 +(CF.sub.2 ═CFCF.sub.2 OCF.sub.2).sub.2 CF.sub.2 →Copolymer

A mixture of perfluoro-1,3-bis(2-propenyloxy)propane (Example 17, 5.7 g,0.013 mol), 1,1,2-trichloro-1,2,2-trifluoroethane (25 ml), and 8%pentafluoropropionyl peroxide in 1,1,2-trichloro-1,2,2-trifluoroethane(5 ml) was held at -40° C. in a stainless steel-lined shaker tube whilevinylidene fluoride (20 g, 0.32 mol) was condensed into the tube. Themixture was shaken overnight at room temperature, and the product wasisolated as described above. The crude polymer was dried under vacuum,pulverized in a blender with 95% ethanol, filtered and dried to give24.0 g of solid copolymer. DSC showed an endotherm Tp 124° C., stable toat least 300° C., indicating that a true copolymer had been formed sincepoly(vinylidene fluoride) has mp 171° C. The insolubility of thisproduct in acetone and the lack of absorption bands in the infrared forpendant CF═CF₂ groups indicates that crosslinking had occurred.

Example K Copolymer of TFE with Methyl Perfluoro-3,6-dioxanon-8-enoate

45 g of methyl perfluoro-3,6-dioxanon-8-enoate and 0.04 g ofperfluoropropionyl peroxide were reacted at 50° C. for 4 hr. under a 10psi pressure of tetrafluoroethylene. Filtration gave a solid which ondrying at 50° C. in a vacuum oven weighed 0.71 g. The amount of TFEadded was 4 g. Equivalent weight by titration gave 1176; therefore theamount of the ester incorporated in the polymer was 28% and the yieldbased on TFE was 20%. A transparent film was obtained by heating at 220°C. in a Carver press.

Example L Dyeable Fluorocarbon Polymers

Samples of the polymers of Examples B and E were treated with aqueousalcoholic ammonia solution for one day at 25° C., filtered, washed withaqueous ethanol and dried under vacuum.

A sample of the polymer of Example C was similarly treated with aqueousalcoholic sodium hydroxide.

The above partly hydrolyzed polymers were immersed in aqueous ethanolsolutions of Sevron® Red GL (Sevron® is a line of cationic dyesespecially suited for dyeing Orlon® and other acrylic fibers, havingoutstanding fastness and brilliance--Du Pont Products Book, January1975, p. 34) at 25° C. for 1-3 hours, then they are extracted until theextracts no longer contained dye. All three samples dyed well to anorange-red color.

Example M Wettable Fluorocarbon Polymer

A sample of the polymer of Example C was treated with aqueous alcoholicsodium hydroxide as described in Example L. The resulting fluorocarbonpolymer contained carbonyl groups and was wettable with water.

Example N Emulsion Polymerization of Tetrafluoroethylene with2-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride

    CF.sub.2 ═CF.sub.2 +CF.sub.2 ═CFCF.sub.2 OCF.sub.2 CF.sub.2 SO.sub.2 F→Copolymer

A stainless steel shaker tube was charged with water (140 ml),1,1,2-trichloro-1,2,2-trifluoroethane (10 ml),2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride(Example 7, 6.0 g), potassium perfluorooctanesulfonate (0.16 g),ammonium carbonate (0.50 g) and ammonium persulfate (0.50 g). Themixture was brought to an internal pressure of 200 p.s.i.g. withtetrafluoroethylene and heated to 70° C. Tetrafluoroethylene pressurewas maintained at 200 p.s.i.g. for 45 min at 70° C. The polymericproduct thus obtained was filtered, washed and dried to give 43.2 g ofwhite solid which contained approximately 1.4 wt % (0.43 mol %) ofpolyfluoroallyloxy comonomer by infrared analysis. Differential thermalanalysis (DTA) showed a crystalline transition at 10° C., a recyclefreezing temperature of 293° C. and a recycle melting point of 311° C.from which the polyfluoroallyloxy comonomer content is estimated as 3.5wt % (1.09 mol %).

Example O Emulsion Polymerization of Tetrafluoroethylene with2-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride

    CF.sub.2 ═CF.sub.2 +CF.sub.2 ═CFCF.sub.2 OCF.sub.2 CF.sub.2 SO.sub.2 F→Copolymer

The procedure of Example N was followed using 8.0 g of2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride,0.20 g of potassium perfluorooctanesulfonate and tetrafluoroethylene ata pressure of 30 p.s.i.g. at 70° C. for a reaction period of 8 hours.The amounts of the other reagents were not changed. This gave 45 g ofsolid polymer whose infrared spectrum showed strong SO₂ F absorption.DTA showed a crystalline transition at 5° C., a recycle freezingtemperature of 282° C., and a recycle melting point of 300° C.,corresponding to a polyfluoroallyloxy comonomer content of 5.9 wt %(1.86 mol %).

Example P Emulsion Polymerization of Tetrafluoroethylene with2-[1-(Pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride

The procedure of Example N was followed using 10.7 g of2-[1-pentafluoro-2-propenyloxy)]tetrafluorosulfonyl fluoride, 0.20 g ofammonium persulfate, and tetrafluoroethylene at a pressure of 50p.s.i.g. at 70° C. for a reaction period of 5 hours. The amounts ofother reagents were not changed. This gave 28.6 g of white polymer whoseinfrared spectrum showed the presence of SO₂ F groups corresponding to3.5 wt % (1.08 mol %) polyfluoroallyloxy comonomer. DTA showed twomelting peaks at 290° C. and 317° C., with an estimated conomomercontent of 5.5 wt % (1.73 mol %).

Utility Example Q Copolymerization of Tetrafluoroethylene and2-[1-(pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl Fluoride, andPreparation of Electrically Conductive Films from the Copolymer Product##STR67##

A steel tube charged with2-[1-pentafluoro-2-propenyloxy)]tetrafluoroethanesulfonyl fluoride(Example 7, 52.8 g) and 6% 1,1,2-trichloro-1,2,2-trifluoroethanesolution of pentafluoropropionyl peroxide initiator (0.19 g). Themixture was heated to 40° C. and brought to an internal pressure of 10psig with tetrafluoroethylene (TFE). TFE pressure was maintained at 10psig for 6 hours at 40° C. The polymeric product thus obtained wasfiltered, washed and dried to give a white solid (9.82 g): λmax (KBr)8.65μ (SO₂ F) and 8-10 mm (broad) in addition to the usualpolytetrafluoroethylene IR bands. The DSC melting point depression was91° C. compared with polytetrafluoroethylene. Sulfur analysis by x-rayfluorescence gave 2.7% S or 28.0 wt. % (8.5 mol %) of polyfluoroallyloxycomonomer, corresponding to an equivalent weight of 1180.

The product was pressed into a clear 4-5 mil film at 220°-240° C. Fourinch diameter film samples were reacted for 1 hour at 90° C. with 13-15%potassium hydroxide solution and dried to give a copolymer of TFE andCF₂ ═CFCF₂ OCF₂ CF₂ SO₃ ⁻ K⁺. IR spectra showed essentially completeconversion of --SO₂ F functions to sulfonate salt.

The four-inch diameter, 4-5 mil film was inserted as the ion exchangemembrane in a chlor-alkali electrolysis cell operated at 2.0 amps/in².Cell voltage and current efficiency were measured as a function of celloperating time and sodium hydroxide concentration. The following resultswere obtained for a 15-day test:

    ______________________________________                                             Sodium Hydroxide                                                                            Current Efficiency                                                                          Cell Voltage                                 Day  Product (%)   (%)           (volts)                                      ______________________________________                                         1   21.5          70.7          3.35                                         10   21.5          71.2          3.45                                         15   30.0          65.2          3.60                                         ______________________________________                                    

Utility Example R Copolymerization of Tetrafluoroethylene andPerfluoro-6-oxanon-8-enoic acid, and Preparation of ElectricallyConductive Films from the Copolymer Product ##STR68##

The procedure of Example Q was followed with perfluoro-6-oxanon-8-enoicacid (47.5 g), 8% pentafluoropropionyl peroxide in1,1,2-trichloro-1,2,2-trifluoroethane (0.05 g), and TFE at 10 psig (40°C.) to give 2.41 g of solid, white copolymer: DSC melting pointdepression was 157° C. compared with polytetrafluoroethylene. Analysisof carboxyl groups by titration showed 36.8 wt. % (9.3 mol %) ofpolyfluoroallyloxy comonomer, corresponding to an equivalent weight of1070.

The copolymer product was pressed into 4-5 mil film and hydrolyzed asdescribed in Example Q. IR spectra showed essentially completeconversion of --COF functions to carboxylate salt, indicating acopolymer of TFE and CF₂ ═CFCF₂ O(CF₂)₄ CO₂ ⁻ K⁺.

A four-inch diameter sample of the 4-5 mil film was inserted as theion-exchange membrane in a chlor-alkali cell operated at 2.0 amps/in²,and the following results were obtained in a 76 day test:

    ______________________________________                                             Sodium Hydroxide                                                                            Current Efficiency                                                                          Cell Voltage                                 Day  Product (%)   (%)           (volts)                                      ______________________________________                                         1   37.1          93.3          4.02                                         20   39.2          90.9          4.60                                         35   39.4          87.7          4.25                                         50   32.9          92.0          4.11                                         76   34.6          85.8          4.67                                         ______________________________________                                    

I claim:
 1. A polyfluoroallyloxy compound having the formula: ##STR69##wherein X is --Cl or --F, and R_(F) is: ##STR70## wherein R¹ is acarbon-carbon bond or a linear or branched perfluoroalkylene group of 1to 12 carbon atoms; Q is --CO₂ H or --CO₂ R⁴ where R⁴ is --CH₃ or --C₂H₅ ; Y and Y', independently, are --F or --CF₃ providing that only oneof Y and Y' can be --CF₃ ; or

    --CF(R.sup.2).sub.2                                        (ii)

wherein R² is --CF₂ CO₂ H, or --CF₂ CO₂ R⁴ where R⁴ is defined as above;or ##STR71## wherein R³ is a linear or branched perfluoroalkylene groupof carbon content such that the moiety ##STR72## does not exceed 15carbon atoms; Y is --F or --CF₃ ; n is 1 to 4; and Q' is defined as forQ above; or ##STR73## wherein G is --CO₂ H or --CO₂ R⁴ where R⁴ is --CH₃or --C₂ H₅.
 2. The polyfluoroallyloxy compound of claim 1 wherein R_(F)is ##STR74##
 3. The polyfluoroallyloxy compound of claim 2 wherein R¹ isa carbon-carbon bond or a linear or branched perfluoroalkylene group of1 to 8 carbon atoms.
 4. The polyfluoroallyloxy compound of claim 3wherein X is --F.
 5. The polyfluoroallyloxy compound of claim 1 whereinR_(F) is --CF(R²)₂.
 6. The polyfluoroallyloxy compound of claim 1wherein R_(F) is ##STR75##
 7. The polyfluoroallyloxy compound of claim 6wherein R_(F) contains up to 8 carbon atoms.